Direct Observation of Enhanced Iodine Binding within a Series of Functionalized Metal-Organic Frameworks with Exceptional Irradiation Stability.

Optimization of active sites and stability under irradiation are important targets for sorbent materials that might be used for iodine (I2) storage. Herein, we report the direct observation of I2 binding in a series of Cu(II)-based isostructural metal-organic frameworks, MFM-170, MFM-172, MFM-174, NJU-Bai20, and NJU-Bai21, incorporating various functional groups (-H, -CH3, - NH2, -C≡C-, and -CONH-, respectively). MFM-170 shows a reversible uptake of 3.37 g g-1 and a high packing density of 4.41 g cm-3 for physiosorbed I2. The incorporation of -NH2 and -C≡C- moieties in MFM-174 and NJU-Bai20, respectively, enhances the binding of I2, affording uptakes of up to 3.91 g g-1. In addition, an exceptional I2 packing density of 4.83 g cm-3 is achieved in MFM-174, comparable to that of solid iodine (4.93 g cm-3). In situ crystallographic studies show the formation of a range of supramolecular and chemical interactions [I···N, I···H2N] and [I···C≡C, I-C═C-I] between -NH2, -C≡C- sites, respectively, and adsorbed I2 molecules. These observations have been confirmed via a combination of solid-state nuclear magnetic resonance, X-ray photoelectron, and Raman spectroscopies. Importantly, γ-irradiation confirmed the ultraresistance of MFM-170, MFM-174, and NJU-Bai20 suggesting their potential as efficient sorbents for cleanup of radioactive waste.

Can children learn verbs from events separated in time? Examining how variability and memory contribute to verb learning.

Children in everyday environments experience verbs separated by minutes or hours and linked to events that vary in their similarity. Prior studies have shown that seeing similar events can be beneficial for verb learning (e.g., complex events), but there is also evidence that varied events or seeing both similar and varied events is useful; more studies are needed. In addition, few prior verb studies have tested verb learning from spaced practice. In Study 1, 3½- and 4½-year-olds (N = 72) saw either three similar events, three varied events, or a single live event (control) while hearing a new verb; events were separated by 1-min delays. Results showed better performance in multiple-event conditions than in the single-event condition and showed more extensions with age. Specifically, children benefitted more from seeing varied events with age. In Study 2, 2½-, 3½-, and 4½-year-olds (N = 163) either saw similar and then varied events or saw all varied video events separated by 1-min delays or no delays. The youngest children performed significantly better in the similar first condition than in the all varied condition, showing the first evidence of this benefit following spaced practice. In addition, as in Study 1, performance after seeing varied events increased with age. Together, these studies show that children can compare events separated in time and that their ability to learn verbs from varied examples develops with age.

Early mobilisation is associated with lower subacute blood pressure and variability in ICH: A retrospective cohort study✰.

BACKGROUND: Very early rehabilitation after stroke appears to worsen outcome, particularly in intracerebral haemorrhage (ICH). Plausible mechanisms include increased mean blood pressure (BP) and BP variability. AIMS: To test associations between early mobilisation, subacute BP and survival, in observational data of ICH patients during routine clinical care. METHODS: We collected demographic, clinical and imaging data from 1372 consecutive spontaneous ICH patients admitted between 2 June 2013 and 28 September 2018. Time to first mobilisation (defined as walking, standing, or sitting out-of-bed) was extracted from electronic records. We evaluated associations between early mobilisation (within 24 h of onset) and both subacute BP and death by 30 days using multifactorial linear and logistic regression analyses respectively. RESULTS: Mobilisation at 24 h was not associated with increased odds of death by 30 days when adjusting for key prognostic factors (OR 0.4, 95% CI 0.2 to 1.1, p = 0.07). Mobilisation at 24 h was independently associated with both lower mean systolic BP (-4.5 mmHg, 95% CI -7.5 to -1.5 mmHg, p = 0.003) and lower diastolic BP variability (-1.3 mmHg, 95% CI -2.4 to -0.2 mg, p = 0.02) during the first 72 h after admission. CONCLUSIONS: Adjusted analysis in this observational dataset did not find an association between early mobilisation and death by 30 days. We found early mobilisation at 24 h to be independently associated with lower mean systolic BP and lower diastolic BP variability over 72 h. Further work is needed to establish mechanisms for the possible detrimental effect of early mobilisation in ICH.

Structural and Dynamic Analysis of Sulphur Dioxide Adsorption in a Series of Zirconium-Based Metal-Organic Frameworks.

We report reversible high capacity adsorption of SO2 in robust Zr-based metal-organic framework (MOF) materials. Zr-bptc (H4 bptc=biphenyl-3,3',5,5'-tetracarboxylic acid) shows a high SO2 uptake of 6.2 mmol g-1 at 0.1 bar and 298 K, reflecting excellent capture capability and removal of SO2 at low concentration (2500 ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically-dispersed CuII or heteroatomic sulphur sites into the pores enhance the capture of SO2 at low concentrations. The captured SO2 can be converted quantitatively to a pharmaceutical intermediate, aryl N-aminosulfonamide, thus converting waste to chemical values. In situ X-ray diffraction, infrared micro-spectroscopy and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO2 molecules and host-guest binding dynamics in these materials at the atomic level. Refinement of the pore environment plays a critical role in designing efficient sorbent materials.

Simultaneous neutron powder diffraction and microwave characterisation at elevated temperatures.

The use of simultaneous neutron powder diffraction (NPD) and microwave characterisation can provide more information than the use of either technique individually; for example, it enables the differentiation of physisorbed and metal-coordinated species. Many possible experiments using these combined techniques can benefit from the addition of a heat source for sample heating, such as real-time measurements of solvent removal, or chemical and catalytic reactions. This paper documents the design of equipment to conduct simultaneous NPD and 2.5 GHz microwave cavity resonance techniques at elevated temperatures and confirms the use of this equipment for successful desolvation of a metal-organic framework (MOF) sample at 150 °C. The high sensitivity of microwave characterisation of lossy and polar materials is demonstrated at levels much lower than those that can be detected using crystallographic techniques.

The Origin of Catalytic Benzylic C-H Oxidation over a Redox-Active Metal-Organic Framework.

Selective oxidation of benzylic C-H compounds to ketones is important for the production of a wide range of fine chemicals, and is often achieved using toxic or precious metal catalysts. Herein, we report the efficient oxidation of benzylic C-H groups in a broad range of substrates under mild conditions over a robust metal-organic framework material, MFM-170, incorporating redox-active [Cu2 II (O2 CR)4 ] paddlewheel nodes. A comprehensive investigation employing electron paramagnetic resonance (EPR) spectroscopy and synchrotron X-ray diffraction has identified the critical role of the paddlewheel moiety in activating the oxidant t BuOOH (tert-butyl hydroperoxide) via partial reduction to [CuII CuI (O2 CR)4 ] species.

Purification of Propylene and Ethylene by a Robust Metal-Organic Framework Mediated by Host-Guest Interactions.

Industrial purification of propylene and ethylene requires cryogenic distillation and selective hydrogenation over palladium catalysts to remove propane, ethane and/or trace amounts of acetylene. Here, we report the excellent separation of equimolar mixtures of propylene/propane and ethylene/ethane, and of a 1/100 mixture of acetylene/ethylene by a highly robust microporous material, MFM-520, under dynamic conditions. In situ synchrotron single crystal X-ray diffraction, inelastic neutron scattering and analysis of adsorption thermodynamic parameters reveal that a series of synergistic host-guest interactions involving hydrogen bonding and π⋅⋅⋅π stacking interactions underpin the cooperative binding of alkenes within the pore. Notably, the optimal pore geometry of the material enables selective accommodation of acetylene. The practical potential of this porous material has been demonstrated by fabricating mixed-matrix membranes comprising MFM-520, Matrimid and PIM-1, and these exhibit not only a high permeability for propylene (≈1984 Barrer), but also a separation factor of 7.8 for an equimolar mixture of propylene/propane at 298 K.

Guest-Controlled Incommensurate Modulation in a Meta-Rigid Metal-Organic Framework Material.

Structural transitions of host systems in response to guest binding dominate many chemical processes. We report an unprecedented type of structural flexibility within a meta-rigid material, MFM-520, which exhibits a reversible periodic-to-aperiodic structural transition resulting from a drastic distortion of a [ZnO4N] node controlled by the specific host-guest interactions. The aperiodic crystal structure of MFM-520 has no three-dimensional (3D) lattice periodicity but shows translational symmetry in higher-dimensional (3 + 2)D space. We have directly visualized the aperiodic state which is induced by incommensurate modulation of the periodic framework of MFM-520·H2O upon dehydration to give MFM-520. Filling MFM-520 with CO2 and SO2 reveals that, while CO2 has a minimal structural influence, SO2 can further modulate the structure incommensurately. MFM-520 shows exceptional selectivity for SO2 under flue-gas desulfurization conditions, and the facile release of captured SO2 from MFM-520 enabled the conversion to valuable sulfonamide products. MFM-520 can thus be used as a highly efficient capture and delivery system for SO2.

Reversible coordinative binding and separation of sulfur dioxide in a robust metal-organic framework with open copper sites.

Emissions of SO2 from flue gas and marine transport have detrimental impacts on the environment and human health, but SO2 is also an important industrial feedstock if it can be recovered, stored and transported efficiently. Here we report the exceptional adsorption and separation of SO2 in a porous material, [Cu2(L)] (H4L = 4',4‴-(pyridine-3,5-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid)), MFM-170. MFM-170 exhibits fully reversible SO2 uptake of 17.5 mmol g-1 at 298 K and 1.0 bar, and the SO2 binding domains for trapped molecules within MFM-170 have been determined. We report the reversible coordination of SO2 to open Cu(II) sites, which contributes to excellent adsorption thermodynamics and selectivities for SO2 binding and facile regeneration of MFM-170 after desorption. MFM-170 is stable to water, acid and base and shows great promise for the dynamic separation of SO2 from simulated flue gas mixtures, as confirmed by breakthrough experiments.

Outcomes and Early Recurrence Following Enzymatic (Collagenase) Treatment of Moderate and Severe Dupuytren Contractures.

PURPOSE: We offer collagenase Clostridium histolyticum (CCH) injections to all patients with a Dupuytren contracture and a palpable cord. We assessed whether more severe contractures respond less well or recur more frequently. METHODS: From a database of 502 CCH injections, 386 (77%) had a complete dataset with minimum 1-year face-to-face follow-up. Contracture severity was assessed using the Tubiana system: grade 1 (27%), grade 2 (49%), grade 3 (19%), and grade 4 (5%). Patients received a single intralesional injection of 0.58 mg CCH followed by manipulation. Finger position was measured at 6 to 12 weeks, 6 months, and 1 year. Failure to break the cord, skin tears, and any adverse events were noted. Recurrence was defined as a failure to maintain any prior correction to within 20°. RESULTS: There were 17 failures (4%) and 6 allergic reactions (1%). We found 31% corrected completely, with approximately half remaining corrected at 1 year. We achieved 43° (95% confidence interval, 40°-46°) correction of combined deformity, with 11° (95% confidence interval, 9°-13°) correction attrition over 1 year. Sixteen percent of treated digits experienced a recurrence with no difference between Tubiana grades, and one-third chose further treatment. Following treatment, Tubiana grade 1 contractures improved by 78% in comparison with higher grade contractures (55%-67% relative correction). By 1 year, all grades had a similar mean 46% relative correction. A complete correction was seen in 61% of grade 1 contractures, with more severe contractures less likely to correct completely (9%-24%). A 31% skin tear rate had no impact on outcome, recurrence, or long-term morbidity. CONCLUSIONS: CCH may treat any Dupuytren cord regardless of severity. Although contracture may recur, few patients pursue further treatment within 1 year. TYPE OF STUDY/LEVEL OF EVIDENCE: Therapeutic IV.

Enhancement of CO2 Uptake and Selectivity in a Metal-Organic Framework by the Incorporation of Thiophene Functionality.

The complex [Zn2(tdc)2dabco] (H2tdc = thiophene-2,5-dicarboxylic acid; dabco = 1,4-diazabicyclooctane) shows a remarkable increase in carbon dioxide (CO2) uptake and CO2/dinitrogen (N2) selectivity compared to the nonthiophene analogue [Zn2(bdc)2dabco] (H2bdc = benzene-1,4-dicarboxylic acid; terephthalic acid). CO2 adsorption at 1 bar for [Zn2(tdc)2dabco] is 67.4 cm3·g-1 (13.2 wt %) at 298 K and 153 cm3·g-1 (30.0 wt %) at 273 K. For [Zn2(bdc)2dabco], the equivalent values are 46 cm3·g-1 (9.0 wt %) and 122 cm3·g-1 (23.9 wt %), respectively. The isosteric heat of adsorption for CO2 in [Zn2(tdc)2dabco] at zero coverage is low (23.65 kJ·mol-1), ensuring facile regeneration of the porous material. Enhancement by the thiophene group on the separation of CO2/N2 gas mixtures has been confirmed by both ideal adsorbate solution theory calculations and dynamic breakthrough experiments. The preferred binding sites of adsorbed CO2 in [Zn2(tdc)2dabco] have been unambiguously determined by in situ single-crystal diffraction studies on CO2-loaded [Zn2(tdc)2dabco], coupled with quantum-chemical calculations. These studies unveil the role of the thiophene moieties in the specific CO2 binding via an induced dipole interaction between CO2 and the sulfur center, confirming that an enhanced CO2 capacity in [Zn2(tdc)2dabco] is achieved without the presence of open metal sites. The experimental data and theoretical insight suggest a viable strategy for improvement of the adsorption properties of already known materials through the incorporation of sulfur-based heterocycles within their porous structures.

Outbreak of Neisseria meningitidis capsular group W among scouts returning from the World Scout Jamboree, Japan, 2015.

The 23rd World Scout Jamboree was held in Japan from 28 July to 8 August 2015 and was attended by over 33,000 scouts from 162 countries. An outbreak of invasive meningococcal disease capsular group W was investigated among participants, with four confirmed cases identified in Scotland, who were all associated with one particular scout unit, and two confirmed cases in Sweden; molecular testing showed the same strain to be responsible for illness in both countries. The report describes the public health action taken to prevent further cases and the different decisions reached with respect to how wide to extend the offer of chemoprophylaxis in the two countries; in Scotland, chemoprophylaxis was offered to the unit of 40 participants to which the four cases belonged and to other close contacts of cases, while in Sweden chemoprophylaxis was offered to all those returning from the Jamboree. The report also describes the international collaboration and communication required to investigate and manage such multinational outbreaks in a timely manner.

Music Therapy Assessment Tool for Awareness in Disorders of Consciousness (MATADOC): Reliability and Validity of a Measure to Assess Awareness in Patients with Disorders of Consciousness.

BACKGROUND: Prolonged Disorders of Consciousness (PDOC) describes a population where a consciousness disorder has persisted for at least four weeks post injury but is still under investigation. Complex motor, sensory, communication, and cognitive impairments cause challenges with diagnosis, assessment, and intervention planning. Developing sensitive, reliable, and valid measures is a central concern. The auditory modality is the most sensitive for identifying awareness; however, the current standardized behavioral measures fail to provide adequate screening and measurement of auditory responsiveness. The Music Therapy Assessment Tool for Awareness in Disorders of Consciousness (MATADOC) is a recently standardized measure for assessment with PDOC; however, psychometric values for two of its subscales require examination. OBJECTIVE: To determine the measurement characteristics and properties of the MATADOC subscales two and three. METHODS: In a convenience sample of 21participants with PDOC, a prospective repeated measures study examined inter-rater reliability (IRR) and test-retest reliability (TRR) for both subscales and internal consistency of subscale two. RESULTS: Overall, the items from the MATADOC subscales two and three demonstrated good agreement across and within assessors, with some variability on two identified items. CONCLUSIONS: The MATADOC is a standardized measure for assessment of auditory responsiveness in PDOC. Psychometric limitations for the two identified items may have resulted from variations in music therapist clinical experience and training, leading to variations in the administration and interpretation of PDOC patient responses to these two MATADOC assessment items. Although its psychometric properties could be improved, the MATADOC's clinimetric properties make it a valuable assessment to guide clinical work for patients with PDOC.

Music therapy assessment tool for awareness in disorders of consciousness (MATADOC): standardisation of the principal subscale to assess awareness in patients with disorders of consciousness.

Establishing valid and reliable measures for use with patients with disorders of consciousness (DOC) following profound brain injury is challenging due to a number of factors including the complex presentation of such patients and assessor variability. The auditory modality has been demonstrated to have greater sensitivity for detecting awareness in DOC patients. However, there are no measures developed to assess auditory responsiveness specifically. The objective of this study was to examine the psychometric properties of the principal subscale of a music therapy assessment tool (MATADOC) developed for use with adult DOC patients. The subscale assesses behavioural domains essential for diagnosis of awareness. Twenty-one adult patients were recruited from a specialist rehabilitation unit. In a prospective study with repeated measures, internal consistency, inter-rater and test-retest reliability and dimensionality were examined. The five-item scale showed satisfactory internal reliability (α = .76) and a strong first principal component. Corrected item-total correlations were all > .45. Inter-rater intra-class correlations (ICCs) ranged from 0.65-1.00 and intra-rater ICCs from 0.77-0.90. Rasch analysis confirmed these impressions of a reliable, unidimensional and homogenous scale. Diagnostic outcomes had 100% agreement with a validated external reference standard. The results indicate that the MATADOC principal subscale provides a new behavioural measure that can contribute to interdisciplinary assessment of awareness with DOC patients.

Biomechanical analysis of combi-hole locking compression plate during fracture healing: A numerical study of screw configuration.

Locking compression plates (LCPs) have become a widely used option for treating femur bone fractures. However, the optimal screw configuration with combi-holes remains a subject of debate. The study aims to create a time-dependent finite element (FE) model to assess the impacts of different screw configurations on LCP fixation stiffness and healing efficiency across four healing stages during a complete fracture healing process. To simulate the healing process, we integrated a time-dependent callus formation mechanism into a FE model of the LCP with combi-holes. Three screw configuration parameters, namely working length, screw number, and screw position, were investigated. Increasing the working length negatively affected axial stiffness and healing efficiency (p < 0.001), while screw number or position had no significant impact (p > 0.01). The time-dependent model displayed a moderate correlation with the conventional time-independent model for axial stiffness and healing efficiency (ρ ≥ 0.733, p ≤ 0.025). The highest healing efficiency (95.2%) was observed in screw configuration C125 during the 4-8-week period. The results provide insights into managing fractures using LCPs with combi-holes over an extended duration. Under axial compressive loading conditions, the use of the C125 screw configuration can enhance callus formation during the 4-12-week period for transverse fractures. When employing the C12345 configuration, it becomes crucial to avoid overconstraint during the 4-8-week period.

Predictors of femoral neck fracture following hip resurfacing: a cadaveric study.

We aimed to establish if radiological parameters, dual energy x-ray absorptiometry (DEXA) and quantitative CT (qCT) could predict the risk of sustaining a femoral neck fracture following hip resurfacing. Twenty-one unilateral fresh frozen femurs were used. Each femur had a plain digital anteroposterior radiograph, DEXA scan and qCT scan. Femurs were then prepared for a Birmingham Hip Resurfacing femoral component and loaded to failure. Results demonstrated that gender and qCT measurements showed strong correlation with failure load. QCT could be used as an individual measure to predict risk of post-operative femoral neck fracture. However, when qCT is unavailable; gender, pre-operative DEXA scan and Neck Width measurements can be used together to assess risk of post-operative femoral neck fracture in patients due to undergo hip resurfacing.

Demystifying Palmar Midcarpal Instability.

Palmar midcarpal instability is an uncommon condition diagnosed clinically with a painful pathognomonic clunk on terminal ulnar deviation of the wrist. Various causes have been described, but congenital laxity of the carpal ligaments is thought to be a key contributor. Treatment commences with conservative measures. This includes proprioceptive training based on more recent concepts on the sensorimotor function of the wrist. When these measures plateau, surgery is considered. The lack of high-level evidence and consensus on its cause continue to hamper our understanding and knowledge of this condition. The purpose of this review is to examine the current evidence to conceptualize this mysterious, yet infrequent phenomenon, and to provide an algorithm on its management.

The Effect of the 2019 Novel Coronavirus Pandemic on Stroke and TIA Patient Admissions: Perspectives and Risk Factors.

BACKGROUND: The 2019 novel coronavirus pandemic has generated concern from stroke specialist centres across the globe. Reductions in stroke admissions have been reported, despite many expecting an increase due to the pro-thrombotic nature of 2019 novel coronavirus. AIMS: To assess the impact of the pandemic and subsequent lockdown on stroke admissions and transient ischaemic attack referrals at the Royal Victoria Infirmary, Newcastle-Upon-Tyne, and additionally on patient behaviours affecting modifiable risk factors or perspectives related to accessing healthcare. METHODS: A single-centre retrospective data analysis was carried out on a "lockdown" cohort of suspected stroke patients admitted between 11 March to 26 May 2020 and a "pre-lockdown" cohort admitted in 2019. Differences in weekly admissions, weekly referrals, onset-to-presentation time and weekly thrombolysis cases were examined. Further analysis interrogated these cohorts separated by Bamford classification and stroke mimics (such as seizure/hemiplegic migraine/functional neurology). A binary-format questionnaire was separately administered to admitted patients from 15 April to 5 June 2020. RESULTS: Significant reductions in weekly posterior circulation infarct (-43%, p = 0.017) and stroke-mimic (-47%, p < 0.001) admissions and weekly referrals diagnosed as non-transient ischaemic attack (-55%, p = 0.002) were observed in the lockdown cohort, with no differences in onset-to-presentation time. Over 25% of questionnaire respondents reported less physical activity, increased isolation and delaying their presentation due to the pandemic. CONCLUSIONS: This study provides evidence of reduced stroke-mimic and posterior circulation infarct admissions. Questionnaire findings suggest that patients need to be informed to ensure they appropriately seek medical advice. Significant communication at the stroke-primary care interface is needed to support referral pathways and management of modifiable risk factors.

Autism Spectrum Disorder in the COVID 19 Era: New Challenges - New Solutions.

This survey explored the support available and the effect of lockdown on children with autism spectrum disorder and their families in India and the United Kingdom. Our findings showed significant problems for children and families due to lockdown. App-based information delivered to parents with support showed encouraging feedback.

A path forward for qualitative research on sustainability in the COVID-19 pandemic.

The unique strengths of qualitative research, through in-depth inquiry and identification of unexpected themes and linkages, is essential to our growing understanding of COVID-19's impacts on the social world and its intersection with sustainability science. However, many challenges-physical, psychological, and ethical in nature-face qualitative researchers during the pandemic, as social distancing and travel restrictions prevent in-person field work. In this paper, we outline the essential contributions of qualitative study to sustainability science, discuss current challenges, and in turn, provide recommendations for researchers.