Strategic development of library reference collections in Higher Education : a case study at Loughborough University Library (UK)

Within the Higher Education sector there have been significant and ongoing changes in the methods utilised by library users to acquire information. In light of this recognition, a study was undertaken by a project team at the University Library, Loughborough University, to determine the most appropriate strategy for developing its extensive collection of printed reference material. Issues of space were a major consideration. The intention was to base subsequent recommendations on evidencebased, democratically obtained data. A largely practical approach was adopted with data collected by means of a series of open meetings, a Step analysis and usage surveys. The subsequent results pointed to a requirement to base future development of the collection on a model comprising low levels of printed material with correspondingly high levels of electronic material and management intervention. The recommendations are currently being implemented at Loughborough and may be appropriate for other academic libraries

The ambient hydration of the aluminophosphate JDF-2 to AlPO-53(A):insights from NMR crystallography

The aluminophosphate (AlPO) JDF-2 is prepared hydro­thermally with methyl­ammonium hydroxide (MAH+·HO-, MAH+ = CH3NH3+), giving rise to a microporous AEN-type framework with occluded MAH+ cations and extra-framework (Al-bound) HO- anions. Despite the presence of these species within its pores, JDF-2 can hydrate upon exposure to atmospheric moisture to give AlPO-53(A), an isostructural material whose crystal structure contains one mol­ecule of H2O per formula unit. This hydration can be reversed by mild heating (such as the frictional heating from magic angle spinning). Previous work has shown good agreement between the NMR parameters obtained experimentally and those calculated from the (optimized) crystal structure of JDF-2. However, several discrepancies are apparent between the experimental NMR parameters for AlPO-53(A) and those calculated from the (optimized) crystal structure (e.g. four 13C resonances are observed, rather than the expected two). The unexpected resonances appear and disappear reversibly with the respective addition and removal of H2O, so clearly arise from AlPO-53(A). We investigate the ambient hydration of JDF-2 using qu­anti­tative 31P MAS NMR to follow the transformation over the course of 3 months. The structures of JDF-2 and AlPO-53(A) are also investigated using a combination of multinuclear solid-state NMR spectroscopy to characterize the samples, and first-principles density functional theory (DFT) calculations to evaluate a range of possible structural models in terms of calculated NMR parameters and energetics. The published structure of JDF-2 is shown to be a good representation of the dehydrated material, but modification of the published structure of AlPO-53(A) is required to provide calculated NMR parameters that are in better agreement with experiment. This modification includes reorientation of all the MAH+ cations and partial occupancy of the H2O sites

Thermal dehydrofluorination of GaPO-34 revealed by NMR crystallography

SEA thanks the Royal Society and the Wolfson Foundation for a merit award. The UK 850 MHz solid-state NMR Facility used in this research 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). We acknowledge support from the Collaborative Computational Project on NMR Crystallography CCP-NC funded by EPSRC (EP/M022501/1).Using a combination of solid-state NMR spectroscopy, powder X-ray diffraction (pXRD), thermogravimetry, and periodic density functional theory (DFT) calculations, we investigate the calcination of the chabazite-type gallophosphate, GaPO-34, prepared with either 1-methylimidazole (mim) or pyridine (py) as the structure-directing agent (SDA) and fluoride as the charge-balancing anion. We demonstrate that, prior to SDA combustion, there is an unusual low-temperature dehydrofluorination step at ∼330 °C for the mim material, but not for the py form. The DFT-derived structure for the dehydrofluorinated intermediate contains pentacoordinate Ga species with Ga–N bonds of 2.04 Å to the mim nitrogen atom, in addition to four Ga–O bonds to neighboring PO4 tetrahedra. This observation is consistent with 71Ga NMR spectroscopy, which shows that one-third of the Ga is pentacoordinate with a large quadrupolar coupling constant of ∼11 MHz. Powder X-ray diffraction measured in situ on heating shows the transient appearance of a distinct crystalline phase between 325 and 425 °C before the characteristic chabazite structure is seen, which is consistent with dehydrofluorination prior to loss of the organic SDA. No such dehydrofluorinated intermediate structure is observed for the py form of GaPO-34, which is ascribed to the lower pKa of pyridinium relative to 1-methylimidazolium.PostprintPostprintPeer reviewe

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

Application of NMR crystallography to highly disordered templated materials : extensive local structural disorder in the gallophosphate GaPO-34A

SEA, DMD, JEH and DM thank the ERC (EU FP7 Consolidator Grant 614290 “EXONMR”) for funding. SEA would like to thank the Royal Society and the Wolfson Foundation for a merit award. The National High Magnetic Field Laboratory is supported by National Science Foundation Cooperative Agreement DMR-1644779 and the State of Florida.We present an NMR crystallographic investigation of two as-made forms of the recently characterised gallophosphate GaPO-34A, which has an unusual framework composition with a Ga : P ratio of 7 : 6 and contains both hydroxide and fluoride anions and either 1-methylimidazolium or pyridinium as the structure-directing agent. We combine previously reported X-ray crystallographic data with solid-state NMR spectroscopy and periodic density functional theory (DFT) calculations to show that the structure contains at least three distinct types of disorder (occupational, compositional and dynamic). The occupational disorder arises from the presence of six anion sites per unit cell, but a total occupancy of these of five, leading to full occupancy of four sites and partial occupancy of the fifth and sixth (which are related by symmetry). The mixture of OH and F present leads to compositional disorder on the occupied anion sites, although the occupancy of some sites by F is calculated to be energetically unfavorable and signals relating to F on these sites are not observed by NMR spectroscopy, confirming that the compositional disorder is not random. Finally, a combination of high-field 71Ga NMR spectroscopy and variable-temperature 13C and 31P NMR experiments shows that the structure directing agents are dynamic on the microsecond timescale, which can be supported by averaging the 31P chemical shifts calculated with the SDA in different orientations. This demonstrates the value of an NMR crystallographic approach, particularly in the case of highly disordered crystalline materials, where the growth of large single crystals for conventional structure determination may not be possible owing to the extent of disorder present.PostprintPeer reviewe

Тепловой баланс помещения с электрической кабельной системой отопления

Solvothermal oxidation of metallic gallium in monoethanolamine for 72 h at 240 °C yields a crystalline sample of γ-Ga₂O₃ (∼30 nm crystallites). While Rietveld refinement (cubic spinel structure, <i>Fd</i>3̅<i>m</i>; <i>a</i> = 8.23760(9) Å) reveals that Ga occupies two pairs of octahedral and tetrahedral sites (ideal spinel and nonspinel), it provides no information about their local distribution, which cannot be statistical owing to the short Ga–Ga contacts produced if neighboring ideal spinel and nonspinel sites are simultaneously occupied. To create an atomistic model to reconcile this situation, a 6 × 6 × 6 supercell of the crystal structure is constructed and refined against neutron total scattering data using a reverse Monte Carlo (RMC) approach. This accounts well for the local as well as long-range structure and reveals significant local distortion in the octahedral sites that resembles the structure of thermodynamically stable β-Ga₂O₃. ⁷¹Ga solid-state NMR results reveal a octahedral:tetrahedral Ga ratio that is consistent with the model obtained from RMC. Nanocrystalline samples of γ-Ga₂O₃ are produced by either a short solvothermal reaction (240 °C for 11 h in diethanolamine; ∼15 nm crystallites) or by precipitation from an ethanolic solution of gallium nitrate (∼5 nm crystallites). For these samples, the Bragg scattering profile is broadened by their smaller crystallite size, consistent with transmission electron microscopy results, and analysis of the relative Bragg peak intensities provides evidence that a greater proportion of tetrahedral versus octahedral sites are filled. In contrast, neutron total scattering shows the same average Ga–O distance with decreasing particle size, consistent with ⁷¹Ga solid-state NMR results that indicate that all samples contain the same overall proportion of octahedral:tetrahedral Ga. It is postulated that increased occupation of tetrahedral sites within the smaller crystallites is balanced by an increased proportion of octahedral surface Ga sites, owing to termination by bound solvent or hydroxide

Cognitive training for freezing of gait in Parkinson's disease: a randomized controlled trial.

The pathophysiological mechanism of freezing of gait (FoG) has been linked to executive dysfunction. Cognitive training (CT) is a non-pharmacological intervention which has been shown to improve executive functioning in Parkinson's disease (PD). This study aimed to explore whether targeted CT can reduce the severity of FoG in PD. Patients with PD who self-reported FoG and were free from dementia were randomly allocated to receive either a CT intervention or an active control. Both groups were clinician-facilitated and conducted twice-weekly for seven weeks. The primary outcome was percentage of time spent frozen during a Timed Up and Go task, assessed both on and off dopaminergic medications. Secondary outcomes included multiple neuropsychological and psychosocial measures. A full analysis was first conducted on all participants randomized, followed by a sample of interest including only those who had objective FoG at baseline, and completed the intervention. Sixty-five patients were randomized into the study. The sample of interest included 20 in the CT group and 18 in the active control group. The primary outcome of percentage time spent frozen during a gait task was significantly improved in the CT group compared to active controls in the on-state. There were no differences in the off-state. Patients who received CT also demonstrated improved processing speed and reduced daytime sleepiness compared to those in the active control. The findings suggest that CT can reduce the severity of FoG in the on-state, however replication in a larger sample is required

Tehnika kao čovjekova ekspanzija

Svrha tehnike kojom se čovjek svakodnevno služi jest olakšavanje života. Čovječji život drugačiji je od ostatka živog svijeta (životinje, biljke); zatvoren je u otvorenosti svijeta i prirode – u kulturi. Pritom tehnika koju čovjek koristi nisu samo oruđa i oružja. Od sredine 20. stoljeća povećava se broj istraživanja u području biotehnologije koja daje uvid u bolje razumijevanje biologije, genetike, a i antropologije, s obzirom na to da područje biotehnologije obuhvaća tehničke i prirodne znanosti. Razvoj biotehnologije zahvaljuje razvoju tehnike koja omogućuje bolji i precizniji uvid u njihove predmete promatranja. Snažni razvoj tehnike, osim pitanja vezanih uz prirodu nje same, donosi i pitanja vezana uz ljudsku prirodu, budući da je čovjek taj koji se koristi tehnikom. Tekst navodi cilj u otvorenosti i razmatranju pitanja vezanih uz probleme na relaciji čovjek – tehnika i njihova suodnosa, te nudi neka njegova viđenja; kakva je čovjekova prirodnost, kako je razvoj tehnike utjecao na njegovo viđenje budućeg svijeta te kako taj budući svijet (u odnosu na prošlo vrijeme) izgleda sada

A multinuclear NMR study of six forms of AlPO-34:structure and motional broadening

We report a study of the CHA-type aluminophosphate AlPO-34, prepared with six different structure-directing agents (SDAs): piperidine (pip), morpholine (mor), pyridine (pyr), 1,4,8,11-tetraazacyclotetradecane (cyclam), 1,3 dimethylimidazolium (dmim) chloride and 1-ethyl-3-methylimidazolium (emim) bromide. Using a combination of solid-state NMR spectroscopy, periodic density functional theory (DFT) calculations and synchrotron X-ray diffraction, we show that, even in crystallographically well-ordered materials such as AlPO-34 with dmim as the SDA, local disorder may be present. For such disordered structures, where it is challenging to use DFT to assign NMR spectra, we show that the 31P isotropic chemical shift can be predicted accurately using the mean P-O bond length and P-O-Al bond angle, in an extension of previous work. Variable-temperature 27Al NMR reveals the presence of microsecond-timescale dynamics in all forms of AlPO- 34, with two different motional regimes observed, depending on whether structural H2O is also present. H2O is detected in AlPO-34 prepared with mor as the SDA, although this material was previously reported as anhydrous, suggesting that this form of AlPO-34 may be hygroscopic despite the presence of the SDAs within the pores

How PETE comes to matter in the performance of social justice education

Background: For over four decades there have been calls for physical education (PE) and physical education teacher education (PETE) to address social inequality and foster social justice. Yet, as numerous studies demonstrate, attempts to educate for social justice in PETE are infrequent and rarely comprehensive. This raises the question why it appears to be possible in some situations but not others, and for some students and not others.    Purpose: The purpose of this paper is to examine the multiple socio-political networks or assemblages in which PETE is embedded and explore how these shape the possibilities for students to engage with the concept of social justice and sociocultural issues when learning to teach PE. Two research questions guided this study: How does an orientation for social justice education within education policy affect the standards for enacting PETE programs? How is social justice education encouraged within PETE programs? Methodology: Methodology: Drawing from a broader study of over 70 key personnel in more than 40 PETE programs, we examined how faculty in PETE understand their professional world, identify their subjective meanings of their experiences, and address sociocultural issues (SCI) and social justice education (SJE) within PETE. Data sources included an initial survey, a semi-structured interview, and program artifacts. We analyze the ways that SJE/SCI was represented in three national settings (England, the United States, and New Zealand) and identified common themes. Results:  Examination of each national setting reveals ways that SJE and SCI were enabled and constrained across the national, programmatic, and individual level in each of the countries. The coherence of explicit National policy and curricula, PETE program philosophies, and the presence of multiple individual interests in social justice served to reify a sociocultural agenda. Conversely possibilities were nullified by narrow or general National Standards, programs that failed to acknowledge sociocultural interests, and the absence of a critical mass of actors with a socio-critical orientation. These differences in assemblage culminated in variations in curriculum time that served to restrict or enable the breadth, frequency, and consistency of the messages surrounding SCI in PETE Conclusion: These findings highlight the importance of acknowledging socio-political networks where PETE operates. The agency of PETEs to enact pedagogies that foreground sociocultural interests is contingent on congruity of the networks. The authors caution that although the ‘perfect storm’ of conditions have a profound influence of the possibility of transformational learning of SCI in PETE, this arrangement is always temporary, fluid, and subject to changes in any of the three network levels. Additionally, the success of PETE in enabling graduating PE teachers to recognize the inequities that may be reinforced through the ‘hidden curriculum’ and to problematize the subject area is contingent on the expectations of the schools in which they teach.