Crystallographic investigation into the self-assembly, guest binding, and flexibility of urea functionalised metal-organic frameworks

Introduction of hydrogen bond functionality into metal-organic frameworks can enhance guest binding and activation, but a combination of linker flexibility and interligand hydrogen bonding often results in the generation of unwanted structures where the functionality is masked. Herein, we describe the self-assembly of three materials, where Cd2+, Ca2+, and Zn2+ are linked by N,Nʹ-bis(4-carboxyphenyl)urea, and examine the effect of the urea units on structure formation, the generation of unusual secondary building units, structural flexibility, and guest binding. The flexibility of the Zn MOF is probed through single-crystal to single-crystal transformations upon exchange of DMF guests for CS2, showing that the lability of the [Zn4O(RCO2)6] cluster towards solvation enables the urea linkers to adopt distorted conformations as the MOF breathes, even facilitating rotation from the trans/trans to the trans/cis conformation without compromising the overall topology. The results have significant implications in the mechanistic understanding of the hydrolytic stability of MOFs, and in preparing heterogeneous organocatalysts

Usefulness of Kinesiotaping for Children Experiencing High Tone and Spasticity as a Symptom of Cerebral Palsy

This critically appraised topic focuses on the use of Kinesiotape for improving occupational engagement for children and adolescents experiencing high tone or spasticity related to the diagnosis of Cerebral Palsy treated in the outpatient setting. To develop a better understanding of the different factors in question, Cerebral Palsy and Kinesiotape are first addressed, then the impacts on the quality of life in children with CP, and finally, occupational therapy\u27s role in the use of Kinesiotape and treatment of CP

The semiquinone radical anion of 1,10-phenanthroline-5,6-dione: synthesis and rare earth coordination chemistry

Reduction of 1,10-phenanthroline-5,6-dione (pd) with CoCpR2 resulted in the first molecular compounds of the pd˙− semi-quinone radical anion, [CoCpR2]+[pd]˙− (R = H, (1); R = Me4, (2)). Furthermore compounds 1 and 2 were reacted with [Y(hfac)3(thf)2] (hfac = 1,1,1-5,5,5-hexafluoroacetylacetonate) to synthesise the rare earth-transition metal heterometallic compounds, [CoCpR2]+[Y(hfac)3(N,N′-pd)]˙− (R = H, (3); R = Me4, (4))

An investigation into the utility of the Mini Addenbrooke's Cognitive Examination (M-ACE) for the early detection of dementia and mild cognitive impairment in people aged 75 and over

Background/Aims: The Mini Addenbrooke’s Cognitive Examination (M-ACE) is the abbreviated version of the widely-used Addenbrooke’s Cognitive Examination (ACE-III), a cognitive screening tool that is used internationally in the assessment of mild cognitive impairment (MCI) and dementia. The objectives of this study were to investigate the diagnostic accuracy of the M-ACE with individuals aged 75 and over to distinguish between those who do and do not have a dementia or MCI, and also to establish whether the cut-off scores recommended by Hsieh et al. (2014) [9] in the original validation study for the M-ACE are optimal for this age group. Methods: The M-ACE was administered to 58 participants (24 with a diagnosis of dementia, 17 with a diagnosis of MCI and 17 healthy controls). The extent to which scores distinguished between groups (dementia, MCI or no diagnosis) was explored using receiver operating characteristic curve analysis. Results: The optimal cut-off for detecting dementia was ≤ 21/30 (score ≤ 21/30 indicating dementia with a sensitivity of 0.95, a specificity of 1 and a positive predictive value of 1) compared to the original higher published cut-off of ≤ 25/30 (sensitivity of 0.95, specificity of 0.70 and a positive predictive value of 0.82 in this sample). Conclusions: The M-ACE has excellent diagnostic accuracy for the detection of dementia in a UK clinical sample. It may be necessary to consider lower cut-offs than those given in the original validation study

Effort testing in dementia assessment: a systematic review

Objective: Interpretation of neuropsychological test data is only valid when appropriate effort has been exerted. Research, however, suggests that neuropsychologists do not always formally test for effort and that this may especially be the case in the context of dementia assessment. This review systematically examined the literature that has investigated the use of both purpose-built and embedded effort-sensitive indices in dementia, mild cognitive impairment (MCI), and healthy control samples. The aim was to determine which tests of effort are most sensitive to suboptimal effort and least sensitive to the type of cognitive impairment seen in dementia. Methods: A systematic search of databases was conducted to October 2017. There was no start date. Results: Twenty-five studies were included for review. The studies were divided into two categories according to methodology. One category of studies (n = 5) was reviewed using a tailored methodological quality rating checklist whilst the remaining studies (n = 20) were reviewed using the Crowe Critical Appraisal Tool (CCAT). Conclusions: The results of this review suggest that PVTs which take a hierarchical approach to effort testing such as the WMT, MSVT, and NV-MSVT are preferable for use with older adults who are under investigation for possible dementia. These tests go above and beyond the traditional pass/fail approach of more traditional tests of effort because they allow the examiner to analyze the examinee’s profile of scores. The methodological limitations and challenges involved in this field of research are discussed

The modular synthesis of rare earth-transition metal heterobimetallic complexes utilizing a redox-active ligand

We report a robust and modular synthetic route to heterometallic rare earth-transition metal complexes. We have used the redox-active bridging ligand 1,10-phenathroline-5,6-dione (pd), which has selective N,N′ or O,O′ binding sites as the template for this synthetic route. The coordination complexes [Ln(hfac)3(N,N’-pd)] (Ln = Y [1], Gd [2]; hfac = hexafluoroacetylacetonate) were synthesised in high yield. These complexes have been fully characterised using a range of spectroscopic techniques. Solid state molecular structures of 1 and 2 have been determined by X-ray crystallography and display different pd binding modes in coordinating and non-coordinating solvents. Complexes 1 and 2 are unusually highly coloured in coordinating solvents, for example the vis-NIR spectrum of 1 in acetonitrile displays an electronic transition centred at 587 nm with an extinction coefficient consistent with significant charge transfer. The reaction between 1 and 2 and VCp2 or VCpt2 (Cpt = tetramethylcyclopentadienyl) resulted in the isolation of the heterobimetallic complexes, [Ln(hfac)3(N,N′-O,O′-pd)VCp2] (Ln = Y [3], Gd [4]) or [Ln(hfac)3(N,N′-O,O′-pd)VCpt2] (Ln = Y [5], Gd [6]). The solid state molecular structures of 3, 5 and 6 have been determined by X-ray crystallography. The spectroscopic data on 3–6 are consistent with oxidation of V(II) to V(IV) and reduction of pd to pd2− in the heterobimetallic complexes. The spin-Hamiltonian parameters from low temperature X-band EPR spectroscopy of 3 and 5 describe a 2A1 ground state, with a V(IV) centre. DFT calculations on 3 are in good agreement with experimental data and confirm the SOMO as the dx2−y2 orbital localised on vanadium

State Legislative Update

The purpose of this Bill is to provide an alternative approach for individuals with a cause of action against a municipality.\u27 Rather than the costly and time-consuming traditional method of hiring an attorney and filing a lawsuit, House Bill 2631 offers individuals an opportunity for Alternative Dispute Resolution ( ADR ) in the form of arbitration. The Bill would allow any individual with a claim in contract or tort against a municipality to require the municipality to submit to the arbitration of the claim. The purpose of House Bill 2631 is to facilitate the resolution of individual claims against a city. However, a fundamental principle of arbitration is that it is a matter of contract, and no party should be forced into the arbitration of a claim which they have not agreed to arbitrate