Flexible macrocycles as versatile supports for catalytically active metal clusters

Here we present three structurally diverse clusters stabilised by the same macrocyclic polyphenol; t-butylcalix[8]arene. This work demonstrates the range of conformations the flexible ligand is capable of adopting, highlighting its versatility in metal coordination. In addition, a Ti complex displays activity for the ring-opening polymerisation of lactide

Magneto-structural studies of an unusual [MnIIIMnIIGdIII(OR)4]4− partial cubane from 2,2′-bis-p-tBu-calix[4]arene

Reaction of 2,2'-bis-p-tBu-calix[4]arene (H8L) with MnCl2·4H2O, GdCl3·6H2O and 2,6-pyridinedimethanol (H2pdm) affords [MnIIIMnIIGdIII(H3L)(pdmH)(pdm)(MeOH)2(dmf)]·3MeCN·dmf (3·3MeCN·dmf) upon vapour diffusion of MeCN into the basic dmf/MeOH mother liquor. 3 crystallises in the tetragonal space group P41212 with the asymmetric unit comprising the entire cluster. The highly unusual core contains a triangular arrangement of MnIIIMnIIGdIII ions housed within a [MnIIIMnIIGdIII(OR)4]4- partial cubane. Magnetic susceptibility and magnetisation data reveal best fit parameters JMn(II)-Mn(III) = +0.415 cm-1, JMn(III)-Gd(III) = +0.221 cm-1, JMn(II)-Gd(III) = -0.258 cm-1 and DMn(III) = -4.139 cm-1. Theoretically derived magnetic exchange interactions, anisotropy parameters, and magneto-structural correlations for 3 are in excellent agreement with the experimental data

Core expansion of bis-calix[4]arene-supported clusters

Stoichiometric control allows for remarkable expansion of the cores of two known bis-calix[4]arene-supported clusters, with concomitant changes to the magnetic properties.</p

Selective signalling of alcohols by a molecular lattice and mechanism of single-crystal-to-single-crystal transformations

Single-crystal-to-single-crystal (SCSC) transformations of molecular materials involving exchange of lattice molecules are becoming commonplace and very relevant in areas like chemical sensing or the pharmaceutical sector. Spin crossover (SCO) complexes could be great candidates to act as molecular chemical sensors using spin switching to signal detection. We describe here the capacity of the Fe(ii) molecular material [Fe(bpp)(H2L)](ClO4)2·C3H6O (bpp and H2L are 2,6-bis-(pyrazol-3-yl)-pyridine type ligands) to have its lattice acetone molecules replaced by certain selected alcohols from the gas phase (MeOH, EtOH or nPrOH but not iPrOH), signalling the process by a spin transition that also changes the colour of the crystals. The magnetic response of the signalling complex depends on the chain length of the alcohol, allowing selective detection. As these molecular exchanges are SCSC processes, the structures of the alcoholates obtained have been determined by single crystal X-ray diffraction (SCXRD). The removal of n-propanol from its host lattice has been quenched in operando at various intermediate stages and studied by SCXRD to unveil crucial details of the mechanism of this SCSC transformation

Saliva microRNA Biomarkers of Cumulative Concussion

Recurrent concussions increase risk for persistent post-concussion symptoms, and may lead to chronic neurocognitive deficits. Little is known about the molecular pathways that contribute to persistent concussion symptoms. We hypothesized that salivary measurement of microribonucleic acids (miRNAs), a class of epitranscriptional molecules implicated in concussion pathophysiology, would provide insights about the molecular cascade resulting from recurrent concussions. This hypothesis was tested in a case-control study involving 13 former professional football athletes with a history of recurrent concussion, and 18 age/sex-matched peers. Molecules of interest were further validated in a cross-sectional study of 310 younger individuals with a history of no concussion (n = 230), a single concussion (n = 56), or recurrent concussions (n = 24). There was no difference in neurocognitive performance between the former professional athletes and their peers, or among younger individuals with varying concussion exposures. However, younger individuals without prior concussion outperformed peers with prior concussion on three balance assessments. Twenty salivary miRNAs differed (adj. p \u3c 0.05) between former professional athletes and their peers. Two of these (miR-28-3p and miR-339-3p) demonstrated relationships (p \u3c 0.05) with the number of prior concussions reported by younger individuals. miR-28-3p and miR-339-5p may play a role in the pathophysiologic mechanism involved in cumulative concussion effects

Diagnosing Mild Traumatic Brain Injury Using Saliva RNA Compared to Cognitive and Balance Testing

BACKGROUND: Early, accurate diagnosis of mild traumatic brain injury (mTBI) can improve clinical outcomes for patients, but mTBI remains difficult to diagnose because of reliance on subjective symptom reports. An objective biomarker could increase diagnostic accuracy and improve clinical outcomes. The aim of this study was to assess the ability of salivary noncoding RNA (ncRNA) to serve as a diagnostic adjunct to current clinical tools. We hypothesized that saliva ncRNA levels would demonstrate comparable accuracy for identifying mTBI as measures of symptom burden, neurocognition, and balance. METHODS: This case‐control study involved 538 individuals. Participants included 251 individuals with mTBI, enrolled ≤14 days postinjury, from 11 clinical sites. Saliva samples (n = 679) were collected at five time points (≤3, 4‐7, 8‐14, 15‐30, and 31‐60 days post‐mTBI). Levels of ncRNAs (microRNAs, small nucleolar RNAs, and piwi‐interacting RNAs) were quantified within each sample using RNA sequencing. The first sample from each mTBI participant was compared to saliva samples from 287 controls. Samples were divided into testing (n = 430; mTBI = 201 and control = 239) and training sets (n = 108; mTBI = 50 and control = 58). The test set was used to identify ncRNA diagnostic candidates and create a diagnostic model. Model accuracy was assessed in the naïve test set. RESULTS: A model utilizing seven ncRNA ratios, along with participant age and chronic headache status, differentiated mTBI and control participants with a cross‐validated area under the curve (AUC) of .857 in the training set (95% CI, .816‐.903) and .823 in the naïve test set. In a subset of participants (n = 321; mTBI = 176 and control = 145) assessed for symptom burden (Post‐Concussion Symptom Scale), as well as neurocognition and balance (ClearEdge System), these clinical measures yielded cross‐validated AUC of .835 (95% CI, .782‐.880) and .853 (95% CI, .803‐.899), respectively. A model employing symptom burden and four neurocognitive measures identified mTBI participants with similar AUC (.888; CI, .845‐.925) as symptom burden and four ncRNAs (.932; 95% CI, .890‐.965). CONCLUSION: Salivary ncRNA levels represent a noninvasive, biologic measure that can aid objective, accurate diagnosis of mTBI

The supportive care needs of women experiencing gynaecological cancer: a Western Australian cross-sectional study

Background: Women diagnosed with gynaecological cancer experience supportive care needs that require care provision to reduce the impact on their lives. International evidence suggests supportive care needs of women with gynaecological cancer are not being met and provision of holistic care is a priority area for action. Knowledge on gynaecological cancer supportive care needs is limited, specifically comparison of needs and cancer gynaecological subtype. Our aim was to identify supportive care needs of Western Australian women experiencing gynaecological cancer, their satisfaction with help and explore associations between participant’s demographic characteristics and identified needs. Methods: A cross-sectional design incorporating a modified version of the Supportive Care Needs Survey - short form (SCNS-SF34) assessed 37 supportive care needs under five domains in conjunction with demographic data. Three hundred and forty three women with gynaecological cancer attending a tertiary public referral hospital completed the survey over 12 months. Statistical analysis was performed using the R environment for statistical computing. A linear regression model was fitted with factor scores for each domain and demographic characteristics as explanatory variables. Results: Three hundred and three women (83%) identified at least one moderate or high level supportive care need. The five highest ranked needs were, ‘being informed about your test results as soon as feasible’ (54.8%), ‘fears about cancer spreading’ (53.7%), ‘being treated like a person not just another case’ (51.9%), ‘being informed about cancer which is under control or diminishing (that is, remission)’ (50.7%), and ‘being adequately informed about the benefits and side-effects of treatments before you choose to have them’ (49.9%). Eight of the top ten needs were from the ‘health system and information’ domain. Associations between supportive care items and demographic variables revealed ‘cancer type’, and ‘time since completion of treatment’ had no impact on level of perceived need for any domain. Conclusions: Western Australian women with gynaecological cancer identified a high level of supportive care needs. The implementation of a supportive care screening tool is recommended to ensure needs are identified and care is patient-centred. Early identification and management of needs may help to reduce the burden on health system resources for managing ongoing needs