Interior Design Studio; Selection of students’ works in academic year 2014/2015 [ed. Dina Vulin Ileković]

Design of a building or a space always starts and ends with the interior, with thinking and developing a sensitivity towards it. Materials, textures, colours of the planes and volumes correspond to the forms and proportions of the human body while aesthetic experience derives from the psychological complexity of the human mind. This publication shows continuity of a high-quality approach to interior design teaching. It clearly illustrates the way the assignment is conceived and presents the results that students achieved in Interior Design Studio in academic year 2014/15. The twelve most successful projects have been selected here for presentation. The content of this publication is effectively organized and presented thus providing good insight into the course activities

Synthesis and polymorphism of mixed aluminium-gallium oxides

DSC is grateful to the EPSRC for award of an industrial CASE studentship, partly funded by Johnson Matthey plc. SEA, DMD and JEH thank the ERC (EU FP7 Consolidator Grant 614290 “EXONMR”) for funding. SEA would also like to thank the Royal Society and Wolfson Foundation for a merit award.The synthesis of a new solidsolution of the oxyhydroxide Ga5–xAlxO7(OH) isinvestigated via solvothermalreaction between gallium acetylacetonate and aluminium isopropoxide in1,4-butanediol at 240 °C. A limited compositional range 0 ≤ x ≤ 1.5 is produced, with the hexagonalunit cell parameters refined from powder X-ray diffraction (XRD) showing alinear contraction in unit cell volume with increasing Al content. Solid-state 27Aland 71Ga NMR spectroscopy show a strong preference for Ga to occupythe tetrahedral sites and Al to occupy the octahedral sites. Using isopropanolas the solvent, g-Ga2–xAlxO3defect spinel solid solutions with x ≤ 1.8 can be prepared at 240 °C in24 hours. These materials are nanocrystalline, as evidenced by their broaddiffraction profiles, but the refined cubic lattice parameter shows a linearrelationship with the Ga:Al content and solid-state NMR spectroscopy again showsa preference for Al to occupy the octahedral sites. Thermal decomposition ofthe Ga5–xAlxO7(OH)occurs via poorly ordered materials that resemble e-Ga2–xAlxO3and k-Ga2–xAlxO3,but g-Ga2–xAlxO3transforms above 750 °C to monoclinic b-Ga2–xAlxO3for 0 ≤ x ≤ 1.3 and to hexagonal a-Ga2–xAlxO3for x = 1.8, with intermediate compositions 1.3 < x < 1.8 giving mixturesof the aand b polymorphs.Solid-state NMR spectroscopy shows only the expected octahedral Al for a-Ga2–xAlxO3and, for b-Ga2–xAlxO3,the ~1:2 ratio of tetrahedral:octahedral Al is in good agreement with Rietveldanalysis of the average structures against powder XRD data. Relative energiescalculated by periodic density functional theory (DFT) confirm that there is a~5.2 kJ mol–1 penalty for tetrahedral rather than octahedral Al inGa5–xAlxO7(OH), whereas this penalty is muchlower (~2.0 kJ mol–1) for b-Ga2–xAlxO3,in good qualitative agreement with the experimental NMR spectra.PostprintPeer reviewe

Phase distribution, composition and disorder in Y2(Hf,Sn)2O7 ceramics : insights from solid-state NMR spectroscopy and first-principles calculations

The authors would like to thank the ERC (EU FP7 Consolidator Grant 614290 “‘EXONMR’”), and EPSRC for support for SS and ASG (EP/L005581/1). SEA would like to thank the Royal Society and Wolfson Foundation for a merit award. We acknowledge support from the Collaborative Computational Project on NMR Crystallography CCP-NC funded by EPSRC (EP/M022501/1).A NMR crystallographic approach, combining 89Y, 119Sn and 17O NMR spectroscopy with X-ray diffraction and first-principles calculations has been used investigate the number and type of phases present, and the local structure and disorder in Y2Hf2–xSnxO7 ceramics. Although a phase change is predicted with increasing Hf content, NMR spectra clearly show the presence of a significant two-phase region, with a Sn-rich pyrochlore and relatively Hf-rich defect fluorite phase co-existing for much of the compositional series. A single-phase pyrochlore is found only for the Sn end member, and a single defect fluorite phase only for x = 0 to 0.2. A solid-solution limit of ~10% is seen for the substitution of Hf into Y2Sn2O7, although no evidence is seen for any cation ordering or antisite disorder in this phase. In the defect fluorite phase there is preferential ordering of oxygen vacancies around Sn, which is only ever seen in a six-coordinate environment. The remaining vacancies are more likely to be associated with Hf than with Y, although this distinction is less apparent at higher Sn concentrations. To acquire 17O NMR spectra samples were post-synthetically exchanged with 17O2(g), although high temperatures (> 900 ºC) were required to ensure uniform enrichment of different chemical species. although these 17O NMR spectra confirm the formation of mixed-metal materials and the presence of two phases, more quantitative analysis is hindered by the overlap of signals from pyrochlore and defect fluorite phases. In all cases, DFT calculations play a vital role in the interpretation and assignment of the NMR spectra, and in understanding the local structure and disorder in these complex multi-phase materials.PostprintPostprintPeer reviewe

Following the unusual breathing behaviour of 17O-enriched mixed-metal (Al,Ga)-MIL-53 using NMR crystallography

The authors would like to thank the ERC (EU FP7 Consolidator Grant 614290 EXONMR and Advanced Grant 787073 ADOR), and EPSRC (EP/N509759/1) for a studentship for CMR. SEA would like to thank the Royal Society and Wolfson Foundation for a merit award. We acknowledge support from the Collaborative Computational Project on NMR Crystallography (CCP-NC) funded by EPSRC (EP/M022501/1) and the UKCP consortium funded by EPSRC (EP/K013564/1). For computational resources we are grateful to the UK Materials and Molecular Modelling Hub, which is partially funded by EPSRC (EP/P020194/1) and the UK HPC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). The research data (and/or materials) supporting this publication can be accessed at DOI: https://doi.org/10.17630/31529c8b-f197-484c-929b-ef993a5bea68.69The breathing behaviour of 17O-enriched (Al,Ga)-MIL-53, a terephthalate-based metal organic framework, has been investigated using a combination of solid-state nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction (PXRD) and first-principles calculations. These reveal that the behaviour observed for as-made, calcined, hydrated and subsequently dehydrated mixed-metal MIL-53 materials differs with composition, but cannot be described as the compositionally weighted average of the breathing behaviour seen for the two end members. Although the form of MIL-53 adopted by the as-made material is independent of metal composition, upon calcination, materials with higher levels of Al adopt an open pore (OP) form, as found for the Al end member, but substitution of Ga results in mixed pore materials, with OP and narrow pore (NP) forms co-existing. Although the Ga end member is prone to decomposition under the calcination conditions used, a low level of Al in the starting synthesis (5%) leads to an OP mixed-metal MOF that is stable to calcination. Upon hydration all materials almost exclusively adopt a closed pore (CP) structure, with strong hydrogen bonding interactions with water leading to two distinct resonances from the carboxylate oxygens in 17O NMR spectra. When dehydrated, different framework structures are found for the two end members, OP for Al- MIL-53 and NP for Ga-MIL-53, with the proportion of NP MOF seen to increase systematically with the Ga content in mixed-metal materials, in contrast to the forms seen upon initial calcination. 17O NMR spectra of mixed-metal MIL-53 materials show an increased preference for clustering of like cations as the Ga content increases. This is not a result of the small-scale dry gel conversion reactions used for enrichment, as a similar cation distribution and clustering is also observed for (Al0.5,Ga0.5)-MIL-53 synthesised hydrothermally and enriched with 17O via post-synthetic steaming.Publisher PDFPeer reviewe

Speckle-pattern visibility of light transmitted through a multimode optical fiber

We show that the reduction in visibility of the speckle pattern obtained from laser light that has been passed through a step-index light guide can be found from a knowledge of the model dispersion of the guide, and the bandwidth of the laser beam

Manganese-catalyzed synthesis of polyketones using hydrogen-borrowing approach

We report here a method of making polyketones from the coupling of diketones and diols using a manganese pincer complex. The methodology allows us to access various polyketones (polyarylalkylketone) containing aryl, alkyl, and ether functionalities, bridging the gap between the two classes of commercially available polyketones: aliphatic polyketones and polyaryletherketones. Using this methodology, 12 polyketones have been synthesized and characterized using various analytical techniques to understand their chemical, physical, morphological, and mechanical properties. Based on previous reports and our studies, we suggest that the polymerization occurs via a hydrogen-borrowing mechanism that involves the dehydrogenation of diols to dialdehyde followed by aldol condensation of dialdehyde with diketones to form chalcone derivatives and their subsequent hydrogenation to form polyarylalkylketones

Site-specific iron substitution in STA-28, a large pore aluminophosphate zeotype prepared using 1,10-phenanthrolines as framework-bound templates

Funding: UK Engineering and Physical Sciences Research Council (Grant Number(s): EP/N50936X/1, EP/S016201/1, EP/S016147/1); The Royal Society (Grant Number(s): INF\R2\192052).An AlPO4 zeotype has been prepared using the aromatic diamine 1,10‐phenanthroline and some of its methylated analogues as templates. In each case the two template N atoms bind to a specific framework Al site to expand its coordination to the unusual octahedral AlO4N2 environment. Furthermore, using this framework‐bound template, Fe atoms can be included selectively at this site in the framework by direct synthesis, as confirmed by annular dark field scanning transmission electron microscopy and Rietveld refinement. Calcination removes the organic molecules to give large pore framework solids, with BET surface areas up to 540 m2 g‐1 and two perpendicular sets of channels that intersect to give pore space connected by 12‐ring openings along all crystallographic directions.Publisher PDFPeer reviewe

Alkaline-Earth Rhodium Hydroxides: Synthesis, Structures, and Thermal Decomposition to Complex Oxides

The rhodium (III) hydrogarnets Ca3Rh2(OH)12 and Sr3Rh2(OH)12 crystallise as polycrystalline powders under hydrothermal conditions at 200°C from RhCl3·3H2O and either Ca(OH)2 or Sr(OH)2 in either 12 M NaOH or KOH. Rietveld refinements against synchrotron powder X-ray diffraction (XRD) data allow the first crystal structures of the two materials to be determined. If BaO2 is used as a reagent and the concentration of hydroxide increased to hydroflux conditions (excess NaOH) then single crystals of a new complex rhodium hydroxide, BaNaRh(OH)6, are formed in a phase-pure sample, with sodium included from the flux. Structure solution from single-crystal XRD data reveals isolated octahedral Rh centres that share hydroxides with 10-coordinate Ba and two independent 8-coordinate Na sites. 23Na magic-angle spinning NMR confirms the presence of the two crystallographically distinct Na sites and also verifies the diamagnetic nature of the sample, expected for Rh(III). The thermal behaviour of the hydroxides on heating in air was investigated using X-ray thermodiffractometry, showing different decomposition pathways for each material. Ca3Rh2(OH)12 yields CaRh2O4 and CaO above 650°C, from which phase-pure CaRh2O4 is isolated by washing with dilute nitric acid, a material previously only reported by high-pressure or high-temperature synthesis. Sr3Rh2(OH)12 decomposes to give a less crystalline material with a powder XRD pattern that is matched to the 2H-layered hexagonal perovskite Sr6Rh5O15, which contains mixed-valent Rh3+/4+, confirmed by Rh K-edge XANES spectroscopy. On heating BaNaRh(OH)6 a complex set of decomposition events takes place via transient phases

An expanded MIL-53-type coordination polymer with a reactive pendant ligand

The authors acknowledge the University of Warwick Undergraduate Research Support Scheme for award of a bursary to TWC. The EPSRC’s UK National Crystallography Service at the University of Southampton is thanked for one of the data sets. The UK 850 MHz solid-state NMR Facility was funded by EPSRC and BBSRC (contract reference PR140003), as well as the University of Warwick including via part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF). SEA would like to thank the ERC (EU FP7 Consolidator Grant 614290 “EXONMR”).A coordination polymer with a structure isoreticular to MIL-53, but containing a divalent metal cation (Co2+ or Mg2+) and a coordinating 4-styrylpyridine-N-oxide ligand, crystallises under solvothermal conditions; the pendant ligand can be brominated, with evidence from powder X-ray diffraction, element mapping and 81Br solid- state NMR for this post-synthesis modification.Publisher PDFPeer reviewe

HOSPITAL PATIENT SAFETY ASSESSMENT EXEMPLIFIED BY THE STANDARDIZED MORTALITY RATES

Sigurnost bolesnika je važni čimbenik kvalitete zdravstvenog sustava, koji je i zakonski propisan. U Zakonu o kvaliteti zdravstvene zaštite i socijalne skrbi defi nirana je sigurnost zdravstvenog postupka, a u Pravilniku o standardima kvalitete zdravstvene zaštite i načinu njihove primjene navedeni su Pokazatelji sigurnosti (Neočekivani neželjeni događaji i Ostali neželjeni događaji). U Ostale neželjene događaje ubraja se i Stopa standardizirane bolničke smrtnosti. Ona je kvantitativni pokazatelj bolesnikove sigurnosti u bolničkom sustavu zdravstvene zaštite i prati se za smrtnost od akutnog infarkta miokarda, moždanog udara i akutnog pankreatitisa unutar 30 dana od prijama u bolnicu. Opisne liste za indikatore sigurnosti propisala je Agencija za kvalitetu u zdravstvu i socijalnoj skrbi. U KBC Sestre milosrdnice se Stope standardizirane bolničke smrtnosti redovito prate i analiziraju. Rezultati upućuju na primjenu dobre kliničke prakse u KBC Sestre milosrdnice i zadovoljavajuću razinu sigurnosti pacijenata od smrtnosti praćene patologije.Patient safety is a legally prescribed, important quality factor of the healthcare system. The safety of medical procedures is defined in the Act on Healthcare Quality, while safety indicators (such as unexpected and other unwanted events) are depicted in the Healthcare Quality Standards and regulations on their usage. The list of safety indicators is determined by the Healthcare and Social Service Agency. Standardized Hospital Mortality Rate falls under “Other unwanted events”, but is also a quantity indicator of patient safety in the hospital healthcare system where it monitors acute myocardial infarction, stroke and acute pancreatitis in the 30-day hospitalization period. At Sestre milosrdnice University Hospital Centre, this indicator has been monitored and analyzed on a regular basis. Monitoring results indicate good clinical practice, as well as a satisfying level of patient safety in relation to the pathology mortality monitored in the mentioned hospital