88 research outputs found
Increased physical fitness is associated with higher executive functioning in people with dementia
Physical fitness (PF) has been associated with improved cognition in older age, but less is known about its effects on different cognitive domains in individuals diagnosed with dementia. We explored the associations between PF and cognitive performance in 40 healthy elderly and 30 individuals with dementia. Participants completed a battery of standardized cognitive tests (Mini-Mental State Exam, Verbal Fluency, Prospective and Retrospective Memory Questionnaire, Clock Drawing, and California Verbal Learning Test) and were classified into high versus low levels of PF based on their score on the Physical Fitness Questionnaire. Analyses took into account age, gender, education, occupation, head injury, Internet use, brain training, and past levels of exercise and revealed overall benefits of PF, in particular for the people with dementia. Discriminant analysis showed high accuracy of reclassification, with most errors being due to the misclassification of dementia cases as healthy when they had high PF. The first discriminant function accounted for 83% of the variance. Using individual estimates of this function, which reflected global cognitive performance, confirmed the beneficial role of PF in dementia, even when taking into account age, past level of exercise, and the number of years since the dementia diagnosis. Finally, univariate analyses confirmed the differential sensitivity of the cognitive tests, with MMSE and clock drawing showing reliable interaction effects. This work shows that PF is associated with a reduced level of cognitive deterioration expected with dementia, especially in executive functioning and provides empirical support for the cognitive benefits of interventions promoting PF for individuals with dementia
Flourescent liquid pyrene derivative-in-water mircoemulsions
A fluorescent liquid pyrene derivative with a high fluorescence quantum yield (65%) in the bulk state is reported. With this as the sole oil phase, stable luminescent oil-in-water microemulsions have been prepared. Increasing the loading of liquid pyrene swells the droplets, as detected by small-angle neutron scattering. These larger droplets have a greater proportion of pyrene excimer emission contribution in their photoluminescence spectra, which leads to a red shift in the chromaticity of the emission
The aggregation of an alkyl-C60 derivative as a function of concentration, temperature and solvent type.
Contrast-variation small-angle neutron scattering (CV-SANS), small-angle X-ray scattering (SAXS), nuclear magnetic resonance (NMR) measurements of diffusion and isothermal titration calorimetry (ITC) are used to gain insight into the aggregation of an alkyl-C60 derivative, molecule 1, in n-hexane, n-decane and toluene as a function of concentration and temperature. Results point to an associative mechanism of aggregation similar to other commonly associating molecules, including non-ionic surfactants or asphaltenes in non-aqueous solvents. Little aggregation is detected in toluene, but small micelle-like structures form in n-alkane solvents, which have a C60-rich core and alkyl-rich shell. The greatest aggregation extent is found in n-hexane, and at 0.1 M the micelles of 1 comprise around 6 molecules at 25 °C. These micelles become smaller when the concentration is lowered, or if the solvent is changed to n-decane. The solution structure is also affected by temperature, with a slightly larger aggregation extent at 10 °C than at 25 °C. At higher concentrations, for example in solutions of 1 above 0.3 M in n-decane, a bicontinuous network becomes apparent. Overall, these findings aid our understanding of the factors driving the assembly of alkyl-p-conjugated hydrophobic amphiphiles such as 1 in solution and thereby represent a step towards the ultimate goal of exploiting this phenomenon to form materials with well-defined order
Diarylethene-Powered Light-Induced Folding of Supramolecular Polymers.
Helical folding of randomly coiled linear polymers is an essential organization process not only for biological polypeptides but also for synthetic functional polymers. Realization of this dynamic process in supramolecular polymers (SPs) is, however, a formidable challenge because of their inherent lability of main chains upon changing an external environment that can drive the folding process (e.g., solvent, concentration, and temperature). We herein report a photoinduced reversible folding/unfolding of rosette-based SPs driven by photoisomerization of a diarylethene (DAE). Temperature-controlled supramolecular polymerization of a barbiturate-functionalized DAE (open isomer) in nonpolar solvent results in the formation of intrinsically curved, but randomly coiled, SPs due to the presence of defects. Irradiation of the randomly coiled SPs with UV light causes efficient ring-closure reaction of the DAE moieties, which induces helical folding of the randomly coiled structures into helicoidal ones, as evidenced by atomic force microscopy and small-angle X-ray scattering. The helical folding is driven by internal structure ordering of the SP fiber that repairs the defects and interloop interaction occurring only for the resulting helicoidal structure. In contrast, direct supramolecular polymerization of the ring-closed DAE monomers by temperature control affords linearly extended ribbon-like SPs lacking intrinsic curvature that are thermodynamically less stable compared to the helicoidal SPs. The finding represents an important concept applicable to other SP systems; that is, postpolymerization (photo)reaction of preorganized kinetic structures can lead to more thermodynamically stable structures that are inaccessible directly through temperature-controlled protocols
Self-assembled poly-catenanes from supramolecular toroidal building blocks
Mechanical interlocking of molecules (catenation) is a nontrivial challenge in modern synthetic chemistry and materials science1,2. One strategy to achieve catenation is the design of pre-annular molecules that are capable of both efficient cyclization and of pre-organizing another precursor to engage in subsequent interlocking3,4,5,6,7,8,9. This task is particularly difficult when the annular target is composed of a large ensemble of molecules, that is, when it is a supramolecular assembly. However, the construction of such unprecedented assemblies would enable the visualization of nontrivial nanotopologies through microscopy techniques, which would not only satisfy academic curiosity but also pave the way to the development of materials with nanotopology-derived properties. Here we report the synthesis of such a nanotopology using fibrous supramolecular assemblies with intrinsic curvature. Using a solvent-mixing strategy, we kinetically organized a molecule that can elongate into toroids with a radius of about 13 nanometres. Atomic force microscopy on the resulting nanoscale toroids revealed a high percentage of catenation, which is sufficient to yield ‘nanolympiadane’10, a nanoscale catenane composed of five interlocked toroids. Spectroscopic and theoretical studies suggested that this unusually high degree of catenation stems from the secondary nucleation of the precursor molecules around the toroids. By modifying the self-assembly protocol to promote ring closure and secondary nucleation, a maximum catenation number of 22 was confirmed by atomic force microscopy
Directed assembly of optoelectronically active alkyl-<i>Ï€</i>-conjugated molecules by adding <i>n</i>-alkanes or <i>Ï€</i>-conjugated species
Supramolecular assembly can yield ordered structures by taking advantage of the cumulative effect of multiple non-covalent interactions between adjacent molecules. The thermodynamic origin of many self-assembled structures in water is the balance between the hydrophilic and hydrophobic segments of the molecule. Here, we show that this approach can be generalized to use solvophobic and solvophilic segments of fully hydrophobic alkylated fullerene molecules. Addition of n-alkanes results in their assembly--due to the antipathy of C60 towards n-alkanes--into micelles and hexagonally packed gel-fibres containing insulated C60 nanowires. The addition of pristine C60 instead directs the assembly into lamellar mesophases by increasing the proportion of π-conjugated material in the mixture. The assembled structures contain a large fraction of optoelectronically active material and exhibit comparably high photoconductivities. This method is shown to be applicable to several alkyl-π-conjugated molecules, and can be used to construct organized functional materials with π-conjugated sections
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Predictors of the experience of a Cytosponge test: analysis of patient survey data from the BEST3 trial
Availability of data and materials: The trial protocol, statistical analysis plan, and statistical report are available via the University of Cambridge data repository (https://www.data.cam.ac.uk/repository). Datasets will be available from R Fitzgerald ([email protected]) on request.Copyright © The Author(s) 2023. Background: The Cytosponge is a cell-collection device, which, coupled with a test for trefoil factor 3 (TFF3), can be used to diagnose Barrett’s oesophagus, a precursor condition to oesophageal adenocarcinoma. BEST3, a large pragmatic, randomised, controlled trial, investigated whether offering the Cytosponge-TFF3 test would increase detection of Barrett’s. Overall, participants reported mostly positive experiences. This study reports the factors associated with the least positive experience. Methods: Patient experience was assessed using the Inventory to Assess Patient Satisfaction (IAPS), a 22-item questionnaire, completed 7–14 days after the Cytosponge test. Study cohort: All BEST3 participants who answered ≥ 15 items of the IAPS (N = 1458). Statistical analysis: A mean IAPS score between 1 and 5 (5 indicates most negative experience) was calculated for each individual. ‘Least positive’ experience was defined according to the 90th percentile. 167 (11.4%) individuals with a mean IAPS score of ≥ 2.32 were included in the ‘least positive’ category and compared with the rest of the cohort. Eleven patient characteristics and one procedure-specific factor were assessed as potential predictors of the least positive experience. Multivariable logistic regression analysis using backwards selection was conducted to identify factors independently associated with the least positive experience and with failed swallow at first attempt, one of the strongest predictors of least positive experience. Results: The majority of responders had a positive experience, with an overall median IAPS score of 1.7 (IQR 1.5–2.1). High (OR = 3.01, 95% CI 2.03–4.46, p < 0.001) or very high (OR = 4.56, 95% CI 2.71–7.66, p < 0.001) anxiety (relative to low/normal anxiety) and a failed swallow at the first attempt (OR = 3.37, 95% CI 2.14–5.30, p < 0.001) were highly significant predictors of the least positive patient experience in multivariable analyses. Additionally, sex (p = 0.036), height (p = 0.032), alcohol intake (p = 0.011) and education level (p = 0.036) were identified as statistically significant predictors. Conclusion: We have identified factors which predict patient experience. Identifying anxiety ahead of the procedure and discussing particular concerns with patients or giving them tips to help with swallowing the capsule might help improve their experience. Trial registration ISRCTN68382401.The BEST3 trial was funded by Cancer Research UK (C14478/A21047), National Institute for Health Research covering service support costs, the UK National Health Service funding excess treatment costs and Medtronic providing funding for Cytosponge devices and TFF3 antibodies. RCF is funded by a Programme Grant from the Medical Research Council (RG84369) and is CI for the BEST3 trial and the Innovate UK funded DELTA study. JO was supported by PDS’s Cancer Research UK programme Grant (C8162/A16892) and is currently supported by the Barts Charity (EMSG1K1R). RM was supported by PDS’ Cancer Research UK Cancer Prevention Clinical Trials Unit funding (Grant No.: C8162/A25356). SGS is supported by a Yorkshire Cancer Research Fellowship. JW is funded by a Cancer Research UK career development fellowship (C7492/A17219). BG was funded as part of the DELTA study by Innovate UK (Grant No. 41162). FW is supported by the Cancer Research UK CanTest Grant [C8640/A23385]. RL is supported by the Intramural Research Program of the US National Institutes of Health/National Cancer Institute
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