The crystal structure of 2-oxo-2H-chromen-4-yl acetate, C11H8O4

C11H8O4, monoclinic, P21/c (no. 14), a = 4.5947(2) Å, b = 10.5414(3) Å, c = 19.1611(7) Å, β = 94.084(2)°, V = 925.70(6) Å3, Z = 4, Rgt(F) = 0.0376, wRref(F 2) = 0.1109,T = 200(2) K.CCDC no.: 190638

The crystal structure of 2-oxo-2H-chromen-4-yl acetate, C11H8O4

C11H8O4, monoclinic, P21/c (no. 14), a = 4.5947(2) Å, b = 10.5414(3) Å, c = 19.1611(7) Å, β = 94.084(2)°, V = 925.70(6) Å3, Z = 4, Rgt(F) = 0.0376, wRref(F 2) = 0.1109,T = 200(2) K.CCDC no.: 190638

Electrocatalytic detection of l-cysteine using molybdenum POM doped-HKUST-1 metal organic frameworks

Glass carbon electrodes (GCE) were modified with metal organic frameworks (MOFs) containing molybdenum polyoxometallates (Mo POMs) in a copper benzene tricarboxylate framework (HKUST-1). The Mo POMs were introduced via one-pot synthesis (Mo2) and post-synthetic modification (Mo1) techniques. The electrode modifiers were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermal analysis. The modified electrodes’ oxidation capacity toward L-cysteine was studied. Mo POMs significantly improved electron transfer kinetics compared to the bare GCE. The best Mo POM doped electrode (Mo1-GCE) had a catalytic rate constant of 2.2 × 104 M−1 s−1 and a limit of detection of 3.07 × 10−7 M. Under the employed experimental conditions, the detection response for L-cysteine was very fast (within 0.1 s) for all the modified electrodes and selective toward L-cysteine in the presence of other amino acids

Photo-and thermoresponsive N-salicylideneaniline derivatives : solid-state studies and structural aspects

Electronic supplementary information (ESI) available. CCDC 1899401, 1902658, 1966932, 1989369, 1989398, 1989403, 2014911, 2014914, 2019418, 2049690, 2049691, 2062423, 2157376, 2156456–2156467 and 2191107–2191119. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi. org/10.1039/d1nj03056f.N-Salicylideneaniline (SA) and its derivatives are known to possess chromism upon exposure to external stimuli. Herein, we present mechanochemical synthesis of a series of photo-and thermoresponsive SA-derivatives and report on solid-state stabilisation of their tautomeric forms either by change in temperature or by photoirradiation. The influence of UV light on proton transfer between the enol-imine (EI) and keto-amine (KA) forms was investigated at λ1 = 254 and λ2 = 365 nm. Differential scanning calorimetry (DSC) measurements provided extra information on the thermodynamic relationship between the prototropic tautomers, and their exposition to liquid nitrogen, combined with variable temperature single-crystal X-ray diffraction (VT-SCXRD) and spectroscopic data, ascertained structural reasons for the intrinsic thermo-optical properties of the compounds. A series of structural determinations between 150 and 300 K further shed light on the thermomechanical behaviour exhibited by the thermoresponsive compounds. By virtue of calorimetry we were able to demonstrate proton transfer via the intramolecular O⋯N hydrogen bond over the temperature range 193–453 K. This present work demonstrates the importance of applying complementary analytical techniques and appropriate approaches for understanding the switching behaviour between the EI and KA forms. Furthermore, the assertion that it is predominantly the planarity (φ < 25°) that determines thermochromaticity is questioned.The National Research Foundation (NRF), South Africa and Rhodes University Research Council.http://rsc.li/njchj2023Chemistr

Cation-/ligand-induced solvent-assisted transformations of Zn(II) and Cu(II) complexes featuring single-pocket multidentate chelating members

A new family of single-pocket metal complexes bearing O,N,O-tridentate and O,N-bidentate chelating members {Cu, 1b (P21/n); Ni, 1c (C2/c); Mn, 1d (I2/a); Cu, 2b; and Ni, 2c (both P21/c)}, starting from synthesized and fully characterized Zn(II) (1a; I2/a) and Cu(II) (2a; C2) precursors, were conveniently prepared via cation-induced solvent-assisted and ligand-induced solvent-assisted transformations. Herein, we show multistep solvent-assisted transformations from cis-1a → trans-1b → cis-1c → cis-1d, as well as all-trans 2a → 2b → 2c. All processes are one-way irreversible, as substantiated by thermodynamic aspects (enthalpies based on Gibbs free energies) derived from density functional theory calculations. On the other hand, complex 2a′ (C2/c; a polymorphic form of 2a) was obtained through a routine synthetic procedure. The compounds have been established by various spectroscopic techniques (infrared, UV−vis, ESI-MS, 1H, and 13C NMR), elemental analysis, and X-ray crystallography. Single-crystal X-ray studies reveal that complexes 1a−d exhibit a pseudo-octahedral geometry around each metal center, with 2a displaying a four-coordinate seesaw geometry Cu(II) sphere (Addison parameter; τ = 0.42), while 2a′ (τ = 0.00), 2b (τ = 0.00), and 2c (τ = 0.00) possess a perfect square-planar configuration around each metal center. Furthermore, distortion is stabilized by the presence of peripheral Odonor atoms from the bulky −OMe group, and by virtue of its size, increased bond lengths and angles are accommodated. Ligand substitution induced coordination geometry transformation from quasi-square-planar 2a to perfect square-planar 2b. Assessment of the metric parameter shows that the distances between the two Cu−Omethoxy are all largely positive due to Jahn−Teller distortion, indicating an unprecedented tetragonal bipyramidal geometry in 1b.The National Research Foundation (NRF, South Africa), Atlantic Philanthropies Scholarship and Rhodes University Research Council.http://pubs.acs.org/journal/cgdefuChemistryNon

Angiomotin and angiomotin like proteins, their expression and correlation with angiogenesis and clinical outcome in human breast cancer

BACKGOUND: Angiomotin is a newly discovered molecule that regulates the migration and tubule formation of endothelial cells. It therefore has been implicated in the control of angiogenesis under physiological and pathological conditions. This study examined the expression of angiomotin and its analogues, angiomotin-like 1 (L1) and -like 2 (L2) in breast tumour tissues, and analysed their correlation with angiogenesis and clinical outcomes. METHODS: Human breast tissues (normal n = 32 and tumours n = 120) were used. The levels of expression of angiomotin, L1 and L2 were determined using reverse transcription PCR. Microvessels were stained using antibodies against PECAM, von Willebrand factor (factor 8, or vWF) and VE-cadherin. The transcript levels of angiomotin and its analogues were assessed against the clinical and pathological background, including long term survival (120 months). RESULTS: Breast cancer tissues expressed significantly higher levels of angiomotin transcript, compared with normal mammary tissues (33.1 ± 11 in normal versus 86.5 ± 13.7 in tumour tissues, p = 0.003). Both L1 and L2 were seen at marginally higher levels in tumour than normal tissues but the difference was not statistically significant. Levels of angiomotin were at significantly higher levels in grade 2 and grade 3 tumours compared with grade 1 (p < 0.01 and p = 0.05 respectively). The levels of angiomotin in tumours from patients who had metastatic disease were also significantly higher than those patients who remained disease free (p = 0.03). Multivariate analysis indicated that angiomotin transcript was an independent prognostic factor (p = 0.031). No significant correlations were seen between angiomotin-L1 and L2 with the clinical outcome. Furthermore, high levels of angiomotin transcript were associated with shorter overall survival (p < 0.05). There was a high degree of correlation between levels of vW factor and that of angiomotin (p < 0.05), but not angiomotin-L1 and angiomotin-L2. CONCLUSION: Angiomotin, a putative endothelial motility factor, is highly expressed in human breast tumour tissues and linked to angiogenesis. It links to the aggressive nature of breast tumours and the long term survival of the patients. These data point angiomotin as being a potential therapeutic target

The use of Enhanced Vegetation Index for assessing access to different types of green space in epidemiological studies

Background: Exposure to green space can protect against poor health through a variety of mechanisms. However, there is heterogeneity in methodological approaches to exposure assessments which makes creating effective policy recommendations challenging. Objective: Critically evaluate the use of a satellite-derived exposure metric, the Enhanced Vegetation Index (EVI), for assessing access to different types of green space in epidemiological studies. Methods: We used Landsat 5–8 (30 m resolution) to calculate average EVI for a 300 m radius surrounding 1.4 million households in Wales, UK for 2018. We calculated two additional measures using topographic vector data to represent access to green spaces within 300 m of household locations. The two topographic vector-based measures were total green space area stratified by type and average private garden size. We used linear regression models to test whether EVI could discriminate between publicly accessible and private green space and Pearson correlation to test associations between EVI and green space types. Results: Mean EVI for a 300 m radius surrounding households in Wales was 0.28 (IQR = 0.12). Total green space area and average private garden size were significantly positively associated with corresponding EVI measures (β = < 0.0001, 95% CI: 0.0000, 0.0000; β = 0.0001, 95% CI: 0.0001, 0.0001 respectively). In urban areas, as average garden size increases by 1 m2, EVI increases by 0.0002. Therefore, in urban areas, to see a 0.1 unit increase in EVI index score, garden size would need to increase by 500 m2. The very small β values represent no ‘measurable real-world’ associations. When stratified by type, we observed no strong associations between greenspace and EVI

Ambient greenness, access to local green spaces, and subsequent mental health: a 10-year longitudinal dynamic panel study of 2·3 million adults in Wales.

BackgroundLiving in greener areas, or close to green and blue spaces (GBS; eg, parks, lakes, or beaches), is associated with better mental health, but longitudinal evidence when GBS exposures precede outcomes is less available. We aimed to analyse the effect of living in or moving to areas with more green space or better access to GBS on subsequent adult mental health over time, while explicitly considering health inequalities.MethodsA cohort of the people in Wales, UK (≥16 years; n=2 341 591) was constructed from electronic health record data sources from Jan 1, 2008 to Oct 31, 2019, comprising 19 141 896 person-years of follow-up. Household ambient greenness (Enhanced Vegetation Index [EVI]), access to GBS (counts, distance to nearest), and common mental health disorders (CMD, based on a validated algorithm combining current diagnoses or symptoms of anxiety or depression [treated or untreated in the preceding 1-year period], or treatment of historical diagnoses from before the current cohort [up to 8 years previously, to 2000], where diagnosis preceded treatment) were record-linked. Cumulative exposure values were created for each adult, censoring for CMD, migration out of Wales, death, or end of cohort. Exposure and CMD associations were evaluated using multivariate logistic regression, stratified by area-level deprivation.FindingsAfter adjustment, exposure to greater ambient greenness over time (+0·1 increased EVI on a 0-1 scale) was associated with lower odds of subsequent CMD (adjusted odds ratio 0·80, 95% CI 0·80-0·81), where CMD was based on a combination of current diagnoses or symptoms (treated or untreated in the preceding 1-year period), or treatments. Ten percentile points more access to GBS was associated with lower odds of a later CMD (0·93, 0·93-0·93). Every additional 360 m to the nearest GBS was associated with higher odds of CMD (1·05, 1·04-1·05). We found that positive effects of GBS on mental health appeared to be greater in more deprived quintiles.InterpretationAmbient exposure is associated with the greatest reduced risk of CMD, particularly for those who live in deprived communities. These findings support authorities responsible for GBS, who are attempting to engage planners and policy makers, to ensure GBS meets residents' needs.FundingNational Institute for Health and Care Research Public Health Research programme

The evolution of non-small cell lung cancer metastases in TRACERx

Metastatic disease is responsible for the majority of cancer-related deaths1. We report the longitudinal evolutionary analysis of 126 non-small cell lung cancer (NSCLC) tumours from 421 prospectively recruited patients in TRACERx who developed metastatic disease, compared with a control cohort of 144 non-metastatic tumours. In 25% of cases, metastases diverged early, before the last clonal sweep in the primary tumour, and early divergence was enriched for patients who were smokers at the time of initial diagnosis. Simulations suggested that early metastatic divergence more frequently occurred at smaller tumour diameters (less than 8 mm). Single-region primary tumour sampling resulted in 83% of late divergence cases being misclassified as early, highlighting the importance of extensive primary tumour sampling. Polyclonal dissemination, which was associated with extrathoracic disease recurrence, was found in 32% of cases. Primary lymph node disease contributed to metastatic relapse in less than 20% of cases, representing a hallmark of metastatic potential rather than a route to subsequent recurrences/disease progression. Metastasis-seeding subclones exhibited subclonal expansions within primary tumours, probably reflecting positive selection. Our findings highlight the importance of selection in metastatic clone evolution within untreated primary tumours, the distinction between monoclonal versus polyclonal seeding in dictating site of recurrence, the limitations of current radiological screening approaches for early diverging tumours and the need to develop strategies to target metastasis-seeding subclones before relaps