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1.
Phys Chem Chem Phys ; 25(42): 28595-28602, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37850329

RESUMO

The potential energy surfaces of pure methanol and mixed methanol-water pentamers have been explored using chirped pulse Fourier-transform microwave spectroscopy aided by ab initio calculations. Rotational constants, anharmonic corrections, dipole moments, and relative energies were calculated for different conformers. Predicted rotational transitions were then fit to experimental spectra from 10-18 GHz and the assignments were confirmed using double resonance experiments where feasible. The results show all 23 of the lowest energy conformers are bound in a planar ring of hydrogen bonding that display a steady decrease in the RO-O distance along this ring as methanol content is increased. Interspersed methanol and water conformers have comparable relative abundances to those with micro-aggregation, but structures with micro-aggregated methanol and water have a higher rigid rotor fitting error. The computational methods' high degree of accuracy when compared to our experimental results suggests the strong donor-acceptor hydrogen bonding in these clusters leads to well-defined minima on the intermolecular potential energy surface.

2.
Phys Chem Chem Phys ; 25(8): 5960-5966, 2023 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-36648367

RESUMO

In an effort to build towards quantitative models of alcohol:water microaggregation in liquid mixtures, the present works characterizes the energy landscape and structures of pure ethanol and mixed ethanol:water tetramers using Chirped Pulse Fourier-transform Microwave spectroscopy. Many conformers of each type of tetramer are available, and those with sufficiently strong dipole moments are experimentally examined. This analysis considers, but does not explicitly fit, the splitting of rotational states due to internal rotation of the methyl groups present, as well as utilizes isotopic substitution experiments to verify the conformer variations observed. Implications of the listed results include a suggestion of the stability of micro-aggregated structures as opposed to homogeneously mixed clusters, informing future work on characterization of larger clusters and any potential modeling of the hydrogen bond network at play.

3.
Phys Chem Chem Phys ; 24(22): 13831-13838, 2022 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-35616604

RESUMO

Here we discuss the design and performance of a novel high-throughput instrument for Chirped Pulse Fourier-transform Microwave (CP-FTMW) spectroscopy, and demonstrate its efficacy through the identification of the lowest energy conformers of the ethanol trimer and mixed water : ethanol trimers. Rotational constants for these trimers were calculated from observed lines in the spectra from 10 to 14 GHz, and compared to the results of anharmonic ab initio computations. As predicted, all trimers share a cyclic donor-acceptor hydrogen bonding structure, with the ethanol monomer favoring the gauche conformation in the lowest energy structures. The increased speed of data collection and resulting sensitivity opens a new avenue into rotational studies of higher order clusters.

4.
BMC Musculoskelet Disord ; 22(1): 672, 2021 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-34372803

RESUMO

BACKGROUND: Unstable ankle fractures represent a substantial burden of disease, accounting for a mean hospital stay of nine days, a mean cost of £4,491 per patient and 20,000 operations per year. There is variation in UK practice around weight-bearing instructions after operatively managed ankle fracture. Early weight-bearing may reduce reliance on health services, time off work, and improve functional outcomes. However, concerns remain about the potential for complications such as implant failure. This is the protocol of a multicentre randomised non-inferiority clinical trial of weight-bearing following operatively treated ankle fracture. METHODS: Adults aged 18 years and over who have been managed operatively for ankle fracture will be assessed for eligibility. Baseline function (Olerud and Molander Ankle Score [OMAS]), health-related quality of life (EQ-5D-5L), and complications will be collected after informed consent has been obtained. A randomisation sequence has been prepared by a trial statistician to allow for 1:1 allocation to receive either instruction to weight-bear as pain allows from the point of randomisation, two weeks after the time of surgery ('early weight-bearing' group) or to not weight-bear for a further four weeks ('delayed weight -bearing' group). All other treatment will be as per the guidance of the treating clinician. Participants will be asked about their weight-bearing status weekly until four weeks post-randomisation. At four weeks post-randomisation complications will be collected. At six weeks, four months, and 12 months post-randomisation, the OMAS, EQ-5D-5L, complications, physiotherapy input, and resource use will be collected. The primary outcome measure is ankle function (OMAS) at four months post-randomisation. A minimum of 436 participants will be recruited to obtain 80% power to detect a non-inferiority margin of -6 points on the OMAS 4 months post-randomisation. A within-trial health economic evaluation will be conducted to estimate the cost-effectiveness of the treatment options. DISCUSSION: The results of this study will inform national guidance with regards to the most clinically and cost-effective strategy for weight-bearing after surgery for unstable ankle fractures. TRIAL REGISTRATION: ISRCTN12883981 , Registered 02 December 2019.


Assuntos
Fraturas do Tornozelo , Adolescente , Adulto , Fraturas do Tornozelo/diagnóstico por imagem , Fraturas do Tornozelo/cirurgia , Articulação do Tornozelo , Humanos , Estudos Multicêntricos como Assunto , Estudos Prospectivos , Qualidade de Vida , Ensaios Clínicos Controlados Aleatórios como Assunto , Resultado do Tratamento , Suporte de Carga
5.
J Phys Condens Matter ; 32(40): 405401, 2020 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-32365341

RESUMO

Pyrrhotite, Fe7S8, is a commonly occurring carrier of magnetic remanence and has a low temperature transition, the Besnus transition, involving a change in spin state. Variations of the thermodynamic, magnetic and elastic properties through this transition at ∼33 K in a natural sample of 4C pyrrhotite have been tested against a group theoretical model for coupling between order parameters relating to Fe/vacancy ordering (irrep U 1(1/2,0,1/4)) and magnetic ordering (irreps m[Formula: see text] and m[Formula: see text]). Magnetoelastic coupling is weak but the pre-existing microstructure of ferroelastic and magnetic domains, that develop as a consequence of Fe/vacancy and ferrimagnetic ordering during slow cooling in nature (P63/mmc → C2'/c'), causes subtle changes in the low temperature transition (C2'/c' → P [Formula: see text]). The Besnus transition involves a rotation of magnetic moments out of the a-c plane of the monoclinic structure, but it appears that the transition temperature might vary locally according to whether it is taking place within the pre-existing domain walls or in the domains that they separate. Evidence of metamagnetic transitions suggests that the magnetic field-temperature phase diagram will display some interesting diversity. Low temperature magnetic transitions in minerals of importance to the palaeomagnetism community have been used to identify the presence of magnetite and haematite in rocks and the Besnus transition is diagnostic of the existence of pyrrhotite, Fe7S8.

6.
Philos Trans A Math Phys Eng Sci ; 377(2149): 20190007, 2019 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-31130099

RESUMO

Magnetic materials with strong local interactions but lacking long-range order have long been a curiosity of physicists. Probing their magnetic interactions is crucial for understanding the unique properties they can exhibit. Metal-organic frameworks have recently gathered more attention as they can produce more exotic structures, allowing for controlled design of magnetic properties not found in conventional metal-oxide materials. Historically, magnetic diffuse scattering in such materials has been overlooked but has attracted greater attention recently, with advances in techniques. In this study, we investigate the magnetic structure of metal-organic formate frameworks, using heat capacity, magnetic susceptibility and neutron diffraction. In Tb(DCO2)3, we observe emergent magnetic order at temperatures below 1.2 K, consisting of two k-vectors. Ho(DCO2)3 shows diffuse scattering above 1.6 K, consistent with ferromagnetic chains packed in a frustrated antiferromagnetic triangular lattice, also observed in Tb(DCO2)3 above 1.2 K. The other lanthanides show no short- or long-range order down to 1.6 K. The results suggest an Ising-like one-dimensional magnetic order associated with frustration is responsible for the magnetocaloric properties, of some members in this family, improving at higher temperatures. This article is part of the theme issue 'Mineralomimesis: natural and synthetic frameworks in science and technology'.

7.
Environ Int ; 127: 305-316, 2019 06.
Artigo em Inglês | MEDLINE | ID: mdl-30953813

RESUMO

BACKGROUND: Exposure to fine particulate matter (PM2.5), an ambient air pollutant with mass-based standards promulgated under the Clean Air Act, and black carbon (BC), a common component of PM2.5, are both associated with cardiovascular health effects. OBJECTIVES: To elucidate whether BC is associated with distinct, or stronger, cardiovascular responses compared to PM2.5, we conducted a systematic review. We evaluated the associations of short- and long-term BC, or the related component elemental carbon (EC), with cardiovascular endpoints including heart rate variability, heart rhythm, blood pressure and vascular function, ST segment depression, repolarization abnormalities, atherosclerosis and heart function, in the context of what is already known about PM2.5. DATA SOURCES: We conducted a stepwise systematic literature search of the PubMed, Web of Science and TOXLINE databases and applied Preferred Reporting Items for Systematic Review and Meta-Analyses (PRISMA) guidelines for reporting our results. STUDY ELIGIBILITY CRITERIA: Studies reporting effect estimates for the association of quantitative measurements of ambient BC (or EC) and PM2.5, with relevant cardiovascular endpoints (i.e. meeting inclusion criteria) were included in the review. Included studies were evaluated for risk of bias in study design and results. STUDY APPRAISAL AND SYNTHESIS METHODS: Risk of bias evaluations assessed aspects of internal validity of study findings based on study design, conduct, and reporting to identify potential issues related to confounding or other biases. Study results are presented to facilitate comparison of the consistency of associations with PM2.5 and BC within and across studies. RESULTS: Our results demonstrate similar associations for BC (or EC) and PM2.5 with the cardiovascular endpoints examined. Across studies, associations for BC and PM2.5 varied in their magnitude and precision, and confidence intervals were generally overlapping within studies. Where differences in the magnitude of the association between BC or EC and PM2.5 within a study could be discerned, no consistent pattern across the studies examined was apparent. LIMITATIONS: We were unable to assess the independence of the effect of BC, relative the effect of PM2.5, on the cardiovascular system, nor was information available to understand the impact of differential exposure misclassification. CONCLUSIONS: Overall, the evidence indicates that both BC (or EC) and PM2.5 are associated with cardiovascular effects but the available evidence is not sufficient to distinguish the effect of BC (or EC) from that of PM2.5 mass.


Assuntos
Carbono/farmacologia , Sistema Cardiovascular/efeitos dos fármacos , Material Particulado/farmacologia , Pressão Sanguínea , Bases de Dados Factuais , Frequência Cardíaca/efeitos dos fármacos , Humanos
8.
Phys Rev Lett ; 122(9): 097201, 2019 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-30932548

RESUMO

We report a comprehensive inelastic neutron-scattering study of the frustrated pyrochlore antiferromagnet MgCr_{2}O_{4} in its cooperative paramagnetic regime. Theoretical modeling yields a microscopic Heisenberg model with exchange interactions up to third-nearest neighbors, which quantitatively explains all of the details of the dynamic magnetic response. Our work demonstrates that the magnetic excitations in paramagnetic MgCr_{2}O_{4} are faithfully represented in the entire Brillouin zone by a theory of magnons propagating in a highly correlated paramagnetic background. Our results also suggest that MgCr_{2}O_{4} is proximate to a spiral spin-liquid phase distinct from the Coulomb phase, which has implications for the magnetostructural phase transition in MgCr_{2}O_{4}.

9.
J Phys Condens Matter ; 31(15): 155401, 2019 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-30641499

RESUMO

The hypothesis that strain has a permeating influence on ferroelastic, magnetic and superconducting transitions in 122 iron pnictides has been tested by investigating variations of the elastic and anelastic properties of a single crystal of Ba(Fe0.957Co0.043)2As2 by resonant ultrasound spectroscopy as a function of temperature and externally applied magnetic field. Non-linear softening and stiffening of C 66 in the stability fields of both the tetragonal and orthorhombic structures has been found to conform quantitatively to the Landau expansion for a pseudoproper ferroelastic transition which is second order in character. The only exception is that the transition occurs at a temperature (T S ≈ 69 K) ~10 K above the temperature at which C 66 would extrapolate to zero ([Formula: see text] ≈ 59 K). An absence of anomalies associated with antiferromagnetic ordering below T N ≈ 60 K implies that coupling of the magnetic order parameter with shear strain is weak. It is concluded that linear-quadratic coupling between the structural/electronic and antiferromagnetic order parameters is suppressed due to the effects of local heterogeneous strain fields arising from the substitution of Fe by Co. An acoustic loss peak at ~50-55 K is attributed to the influence of mobile ferroelastic twin walls that become pinned by a thermally activated process involving polaronic defects. Softening of C 66 by up to ~6% below the normal-superconducting transition at T c ≈ 13 K demonstrates an effective coupling of the shear strain with the order parameter for the superconducting transition which arises indirectly as a consequence of unfavourable coupling of the superconducting order parameter with the ferroelastic order parameter. Ba(Fe0.957Co0.043)2As2 is representative of 122 pnictides as forming a class of multiferroic superconductors in which elastic strain relaxations underpin almost all aspects of coupling between the structural, magnetic and superconducting order parameters and of dynamic properties of the transformation microstructures they contain.

10.
J Phys Condens Matter ; 31(13): 135403, 2019 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-30605895

RESUMO

The elastic and anelastic properties of a single crystal of Co-doped pnictide Ba(Fe0.957Co0.043)2As2 have been determined by resonant ultrasound spectroscopy in the frequency range 10-500 kHz, both as a function of temperature through the normal-superconducting transition (T c ≈ 12.5 K) and as a function of applied magnetic field up to 12.5 T. Correlation with thermal expansion, electrical resistivity, heat capacity, DC and AC magnetic data from crystals taken from the same synthetic batch has revealed the permeating influence of strain on coupling between order parameters for the ferroelastic (Q E) and superconducting (Q SC) transitions and on the freezing/relaxation behaviour of vortices. Elastic softening through T c in zero field can be understood in terms of classical coupling of the order parameter with the shear strain e 6, λe 6 [Formula: see text], which means that there must be a common strain mechanism for coupling of the form λ [Formula: see text] Q E. At fields of ~5 T and above, this softening is masked by Debye-like stiffening and acoustic loss processes due to vortex freezing. The first loss peak may be associated with the establishment of superconductivity on ferroelastic twin walls ahead of the matrix and the second is due to the vortex liquid-vortex glass transition. Strain contrast between vortex cores and the superconducting matrix will contribute significantly to interactions of vortices both with each other and with the underlying crystal structure. These interactions imply that iron-pnictides represent a class of multiferroic superconductors in which strain-mediated coupling occurs between the multiferroic properties (ferroelasticity, antiferromagnetism) and superconductivity.

11.
Qual Life Res ; 28(2): 335-343, 2019 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-30229533

RESUMO

PURPOSE: The Western Ontario and McMaster Universities Arthritis Index (WOMAC) is a commonly used outcome measure for osteoarthritis. There are different versions of the WOMAC (Likert, visual analogue or numeric scales). A previous review of trials published before 2010 found poor reporting and inconsistency in how the WOMAC was used. This review explores whether these problems persist. METHODS: This systematic review included randomised trials of hip and/or knee osteoarthritis published in 2016 that used the WOMAC. Data were extracted on the version used, score range, analysis and results of the WOMAC, and whether these details were clearly reported. RESULTS: This review included 62 trials and 41 reported the WOMAC total score. The version used and item range for the WOMAC total score were unclear in 44% (n = 18/41) and 24% (n = 10/41) of trials, respectively. The smallest total score range was 0-10 (calculated by averaging 24 items scored 0-10); the largest was 0-2400 (calculated by summing 24 items scored 0-100). All trials reported the statistical analysis methods but only 29% reported the between-group mean difference and 95% confidence interval. CONCLUSION: Details on the use and scoring of the WOMAC were often not reported. We recommend that trials report the version of the WOMAC and the score range used. The between-group treatment effect and corresponding confidence interval should be reported. If all the items of the WOMAC are collected, the total score and individual subscale scores should be presented. Better reporting would facilitate the interpretation, comparison and synthesis of the WOMAC score in trials.


Assuntos
Osteoartrite do Quadril/diagnóstico , Osteoartrite do Joelho/diagnóstico , Qualidade de Vida/psicologia , Feminino , Humanos , Masculino , Ontário , Avaliação de Resultados em Cuidados de Saúde
12.
Aliment Pharmacol Ther ; 48(2): 114-126, 2018 07.
Artigo em Inglês | MEDLINE | ID: mdl-29851091

RESUMO

BACKGROUND: Aminosalicylates are the most frequently prescribed drugs for patients with Crohn's disease (CD), yet evidence to support their efficacy as induction or maintenance therapy is controversial. AIMS: To quantify aminosalicylate use in CD clinical trials, identify factors associated with use and estimate direct annual treatment costs of therapy. METHODS: MEDLINE, Embase and CENTRAL were searched to April 2017 for placebo-controlled trials in adults with CD treated with corticosteroids, immunosuppressants or biologics. The proportion of patients co-prescribed aminosalicylates in placebo arms was pooled using a random-effects model. Meta-regression was used to identify factors associated with aminosalicylate use. Annual treatment costs were estimated using the 2016 Ontario Drug Benefit Program. RESULTS: Forty-two induction and 10 maintenance trials were included. The pooled proportion of patients co-prescribed aminosalicylates was 44% [95% CI: 39%-49%] in induction trials and 49% [95% CI: 35%-64%] in maintenance trials. There was substantial to considerable heterogeneity (I2  = 86.0%, 91.8% for induction and maintenance trials, respectively). In multivariable meta-regression, aminosalicylate use has decreased over time in induction trials (OR 0.50 [95% CI: 0.34-0.74] per 10-year increment). While a decline has been seen over time, 35% of CD patients were still using aminosalicylates in contemporary trials from the last 5 years. The estimated annual cost for the lowest price mesalazine (mesalamine) formulation is approximately $32 million for the Canadian CD population. CONCLUSIONS: Over one-third of CD patients entering clinical trials are still co-prescribed aminosalicylates. A definitive trial is needed to inform the conventional practice of using aminosalicylates as CD maintenance therapy.


Assuntos
Doença de Crohn/tratamento farmacológico , Doença de Crohn/economia , Doença de Crohn/epidemiologia , Mesalamina/economia , Mesalamina/uso terapêutico , Corticosteroides/administração & dosagem , Corticosteroides/efeitos adversos , Corticosteroides/economia , Adulto , Produtos Biológicos/administração & dosagem , Produtos Biológicos/efeitos adversos , Produtos Biológicos/economia , Custos de Medicamentos , Quimioterapia Combinada/economia , Quimioterapia Combinada/estatística & dados numéricos , Humanos , Imunossupressores/administração & dosagem , Imunossupressores/efeitos adversos , Imunossupressores/economia , Ontário/epidemiologia , Padrões de Prática Médica/economia , Padrões de Prática Médica/estatística & dados numéricos , Prevalência , Indução de Remissão , Fatores de Risco
13.
J Phys Condens Matter ; 29(40): 405807, 2017 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-28731423

RESUMO

The bulk magnetic properties of the lanthanide metaborates, Ln(BO2)3, Ln = Pr, Nd, Gd, Tb are studied using magnetic susceptibility, heat capacity and isothermal magnetisation measurements. They are found to crystallise in a monoclinic structure containing chains of magnetic Ln 3+ and could therefore exhibit features of low-dimensional magnetism and frustration. Pr(BO2)3 is found to have a non-magnetic singlet ground state. No magnetic ordering is observed down to 0.4 K for Nd(BO2)3. Gd(BO2)3 exhibits a sharp magnetic transition at 1.1 K, corresponding to 3D magnetic ordering. Tb(BO2)3 shows two magnetic ordering features at 1.05 K and 1.95 K. A magnetisation plateau at a third of the saturation magnetisation is seen at 2 K for both Nd(BO2)3 and Tb(BO2)3, which persists in an applied field of 14 T. This is proposed to be a signature of quasi 1D behaviour in Nd(BO2)3 and Tb(BO2)3.

14.
J Phys Condens Matter ; 29(40): 405808, 2017 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-28726675

RESUMO

A systematic study of the structural and magnetic properties of three-dimensionally frustrated lanthanide garnets Ln 3 A 2 X 3O12, Ln = Gd, Tb, Dy, Ho, A = Ga, Sc, In, Te, X = Ga, Al, Li is presented. Garnets with Ln = Gd show magnetic behaviour consistent with isotropic Gd3+ spins; no magnetic ordering is observed for T ⩾ 0.4 K. Magnetic ordering features are seen for garnets with Ln = Tb, Dy, Ho in the temperature range 0.4 < T < 2.5 K, however the nature of the magnetic ordering varies for the different Ln as well as for different combinations of A and X. The magnetic behaviour can be explained by tuning of the magnetic interactions and changes in the single-ion anisotropy. The change in magnetic entropy is evaluated from isothermal magnetisation measurements to characterise the magnetocaloric effect in these materials. Among the Gd garnets, the maximum change in magnetic entropy per mole (15.45 J K-1 [Formula: see text]) is observed for Gd3Sc2Ga3O12 at 2 K, in a field of 9 T. The performance of Dy3Ga5O12 as a magnetocaloric material surpasses the other garnets with Ln = Tb, Dy, Ho.

15.
J Mater Sci ; 52(1): 285-304, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-27829689

RESUMO

Elastic and anelastic properties of ceramic samples of multiferroic perovskites with nominal compositions across the binary join PbZr0.53Ti0.47O3-PbFe0.5Ta0.5O3 (PZT-PFT) have been assembled to create a binary phase diagram and to address the role of strain relaxation associated with their phase transitions. Structural relationships are similar to those observed previously for PbZr0.53Ti0.47O3-PbFe0.5Nb0.5O3 (PZT-PFN), but the magnitude of the tetragonal shear strain associated with the ferroelectric order parameter appears to be much smaller. This leads to relaxor character for the development of ferroelectric properties in the end member PbFe0.5Ta0.5O3. As for PZT-PFN, there appear to be two discrete instabilities rather than simply a reorientation of the electric dipole in the transition sequence cubic-tetragonal-monoclinic, and the second transition has characteristics typical of an improper ferroelastic. At intermediate compositions, the ferroelastic microstructure has strain heterogeneities on a mesoscopic length scale and, probably, also on a microscopic scale. This results in a wide anelastic freezing interval for strain-related defects rather than the freezing of discrete twin walls that would occur in a conventional ferroelastic material. In PFT, however, the acoustic loss behaviour more nearly resembles that due to freezing of conventional ferroelastic twin walls. Precursor softening of the shear modulus in both PFT and PFN does not fit with a Vogel-Fulcher description, but in PFT there is a temperature interval where the softening conforms to a power law suggestive of the role of fluctuations of the order parameter with dispersion along one branch of the Brillouin zone. Magnetic ordering appears to be coupled only weakly with a volume strain and not with shear strain but, as with multiferroic PZT-PFN perovskites, takes place within crystals which have significant strain heterogeneities on different length scales.

16.
Nat Commun ; 7: 13842, 2016 12 20.
Artigo em Inglês | MEDLINE | ID: mdl-27996012

RESUMO

The Ising model-in which degrees of freedom (spins) are binary valued (up/down)-is a cornerstone of statistical physics that shows rich behaviour when spins occupy a highly frustrated lattice such as kagome. Here we show that the layered Ising magnet Dy3Mg2Sb3O14 hosts an emergent order predicted theoretically for individual kagome layers of in-plane Ising spins. Neutron-scattering and bulk thermomagnetic measurements reveal a phase transition at ∼0.3 K from a disordered spin-ice-like regime to an emergent charge ordered state, in which emergent magnetic charge degrees of freedom exhibit three-dimensional order while spins remain partially disordered. Monte Carlo simulations show that an interplay of inter-layer interactions, spin canting and chemical disorder stabilizes this state. Our results establish Dy3Mg2Sb3O14 as a tuneable system to study interacting emergent charges arising from kagome Ising frustration.

17.
J Phys Condens Matter ; 27(28): 285901, 2015 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-26125192

RESUMO

Resonant Ultrasound Spectroscopy has been used to characterize elastic and anelastic anomalies in a polycrystalline sample of multiferroic Pb(Fe(0.5)Nb(0.5))O(3) (PFN). Elastic softening begins at ~550 K, which is close to the Burns temperature marking the development of dynamical polar nanoregions. A small increase in acoustic loss at ~425 K coincides with the value of T(*) reported for polar nanoregions starting to acquire a static or quasi-static component. Softening of the shear modulus by ~30-35% through ~395-320 K, together with a peak in acoustic loss, is due to classical strain/order parameter coupling through the cubic → tetragonal → monoclinic transition sequence of ferroelectric/ferroelastic transitions. A plateau of high acoustic loss below ~320 K is due to the mobility under stress of a ferroelastic microstructure but, instead of the typical effects of freezing of twin wall motion at some low temperature, there is a steady decrease in loss and increase in elastic stiffness below ~85 K. This is attributed to freezing of a succession of strain-coupled defects with a range of relaxation times and is consistent with a report in the literature that PFN develops a tweed microstructure over a wide temperature interval. No overt anomaly was observed near the expected Néel point, ~145 K, consistent with weak/absent spin/lattice coupling but heat capacity measurements showed that the antiferromagnetic transition is actually smeared out or suppressed. Instead, the sample is weakly ferromagnetic up to ~560 K, though it has not been possible to exclude definitively the possibility that this could be due to some magnetic impurity. Overall, evidence from the RUS data is of a permeating influence of static and dynamic strain relaxation effects which are attributed to local strain heterogeneity on a mesoscopic length scale. These, in turn, must have a role in determining the magnetic properties and multiferroic character of PFN.

18.
Colorectal Dis ; 17(11): O217-29, 2015 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-26058878

RESUMO

AIM: Patient-reported outcome (PRO) measures (PROMs) are standard measures in the assessment of colorectal cancer (CRC) treatment, but the range and complexity of available PROMs may be hindering the synthesis of evidence. This systematic review aimed to: (i) summarize PROMs in studies of CRC surgery and (ii) categorize PRO content to inform the future development of an agreed minimum 'core' outcome set to be measured in all trials. METHOD: All PROMs were identified from a systematic review of prospective CRC surgical studies. The type and frequency of PROMs in each study were summarized, and the number of items documented. All items were extracted and independently categorized by content by two researchers into 'health domains', and discrepancies were discussed with a patient and expert. Domain popularity and the distribution of items were summarized. RESULTS: Fifty-eight different PROMs were identified from the 104 included studies. There were 23 generic, four cancer-specific, 11 disease-specific and 16 symptom-specific questionnaires, and three ad hoc measures. The most frequently used PROM was the EORTC QLQ-C30 (50 studies), and most PROMs (n = 40, 69%) were used in only one study. Detailed examination of the 50 available measures identified 917 items, which were categorized into 51 domains. The domains comprising the most items were 'anxiety' (n = 85, 9.2%), 'fatigue' (n = 67, 7.3%) and 'physical function' (n = 63, 6.9%). No domains were included in all PROMs. CONCLUSION: There is major heterogeneity of PRO measurement and a wide variation in content assessed in the PROMs available for CRC. A core outcome set will improve PRO outcome measurement and reporting in CRC trials.


Assuntos
Neoplasias Colorretais/cirurgia , Cirurgia Colorretal/métodos , Avaliação de Resultados da Assistência ao Paciente , Autorrelato , Inquéritos e Questionários , Humanos
19.
Indoor Air ; 25(1): 93-104, 2015 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-24809924

RESUMO

This research assesses benefits of adding to California Title-24 ventilation rate (VR) standards a performance-based option, similar to the American Society of Heating, Refrigerating, and Air Conditioning Engineers 'Indoor Air Quality Procedure' (IAQP) for retail spaces. Ventilation rates and concentrations of contaminants of concern (CoC) were measured in 13 stores. Mass balance models were used to estimate 'IAQP-based' VRs that would maintain concentrations of all CoCs below health- or odor-based reference concentration limits. An intervention study in a 'big box' store assessed how the current VR, the Title 24-prescribed VR, and the IAQP-based VR (0.24, 0.69, and 1.51 air changes per hour) influenced measured IAQ and perceived of IAQ. Neither current VRs nor Title 24-prescribed VRs would maintain all CoCs below reference limits in 12 of 13 stores. In the big box store, the IAQP-based VR kept all CoCs below limits. More than 80% of subjects reported acceptable air quality at all three VRs. In 11 of 13 buildings, saving energy through lower VRs while maintaining acceptable IAQ would require source reduction or gas-phase air cleaning for CoCs. In only one of the 13 retail stores surveyed, application of the IAQP would have allowed reduced VRs without additional contaminant-reduction strategies.


Assuntos
Poluentes Atmosféricos , Poluição do Ar em Ambientes Fechados , Ventilação/normas , Adolescente , Poluentes Atmosféricos/análise , Poluição do Ar em Ambientes Fechados/análise , Aldeídos/análise , California , Comércio , Monitoramento Ambiental/métodos , Feminino , Inquéritos Epidemiológicos , Humanos , Masculino , Percepção , Compostos Orgânicos Voláteis/análise , Adulto Jovem
20.
Bone Joint Res ; 3(11): 321-7, 2014 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-25431439

RESUMO

AIMS: Femoroacetabular Junction Impingement (FAI) describes abnormalities in the shape of the femoral head-neck junction, or abnormalities in the orientation of the acetabulum. In the short term, FAI can give rise to pain and disability, and in the long-term it significantly increases the risk of developing osteoarthritis. The Femoroacetabular Impingement Trial (FAIT) aims to determine whether operative or non-operative intervention is more effective at improving symptoms and preventing the development and progression of osteoarthritis. METHODS: FAIT is a multicentre superiority parallel two-arm randomised controlled trial comparing physiotherapy and activity modification with arthroscopic surgery for the treatment of symptomatic FAI. Patients aged 18 to 60 with clinical and radiological evidence of FAI are eligible. Principal exclusion criteria include previous surgery to the index hip, established osteoarthritis (Kellgren-Lawrence ≥ 2), hip dysplasia (centre-edge angle < 20°), and completion of a physiotherapy programme targeting FAI within the previous 12 months. Recruitment will take place over 24 months and 120 patients will be randomised in a 1:1 ratio and followed up for three years. The two primary outcome measures are change in hip outcome score eight months post-randomisation (approximately six-months post-intervention initiation) and change in radiographic minimum joint space width 38 months post-randomisation. ClinicalTrials.gov: NCT01893034. Cite this article: Bone Joint Res 2014;3:321-7.

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