Mechanism For Copper(II)-Mediated Disaggregation Of A Porphyrin J-Aggregate

J-aggregates of anionic meso-tetrakis(4-sulfonatophenyl)porphyrin form at intermediate pH (2.3–3.1) in the presence of NiSO₄ or ZnSO₄ (ionic strength, I.S. = 3.2 M). These aggregates convert to monomeric porphyrin units via metallation with copper(II) ions. The kinetics for the disassembly process, as monitored by UV/vis spectroscopy, exhibits zeroth-order behavior. The observed zeroth-order rate constants show a two-term dependence on copper(II) ion concentrations: linear and second order. Also observed is an inverse dependence on hydrogen ion concentration. Activation parameters have been determined for the disassembly process leading to ΔH^≠ = (+163 ± 15) kJ·mol⁻¹ and ΔS^≠ = (+136 ± 11) J·K⁻¹. A mechanism is proposed in which copper(II) cation is in pre-equilibrium with a reactive site at the rim of the J-aggregate. An intermediate copper species is thus formed that eventually leads to the final metallated porphyrin either through an assisted attack of a second metal ion or through a direct insertion of the metal cation into the macrocycle core

Coherent electronic and nuclear dynamics in a rhodamine heterodimer-DNA supramolecular complex

Elucidating the role of quantum coherences in energy migration within biological and artificial multichromophoric antenna systems is the subject of an intense debate. It is also a practical matter because of the decisive implications for understanding the biological processes and engineering artificial materials for solar energy harvesting. A supramolecular rhodamine heterodimer on a DNA scaffold was suitably engineered to mimic the basic donor-acceptor unit of light-harvesting antennas. Ultrafast 2D electronic spectroscopic measurements allowed identifying clear features attributable to a coherent superposition of dimer electronic and vibrational states contributing to the coherent electronic charge beating between the donor and the acceptor. The frequency of electronic charge beating is found to be 970 cm-1 (34 fs) and can be observed for 150 fs. Through the support of high level ab initio TD-DFT computations of the entire dimer, we established that the vibrational modes preferentially optically accessed do not drive subsequent coupling between the electronic states on the 600 fs of the experiment. It was thereby possible to characterize the time scales of the early time femtosecond dynamics of the electronic coherence built by the optical excitation in a large rigid supramolecular system at a room temperature in solution. © 2017 the Owner Societies.Multi valued and parallel molecular logi

Quantification of play behaviour in farmed calves using automated ultra-wide band location data and its association with age, weaning and health status

Play behaviour can act as an indicator of positive animal welfare. Previous attempts to predict play behaviour in farmed calves are limited because of the classification methods used, which lead to overestimation, and the short time periods that calves are observed. The study aimed to automatically classify and quantify play behaviour in farmed calves using location data from ultra-wide band sensors and to investigate factors associated with play behaviour. Location data were collected from 46 calves in three cohorts for a period of 18 weeks. Behavioural observations from video footage were merged with location data to obtain a total of 101.36 h of labelled data. An AdaBoost ensemble learning algorithm was implemented to classify play behaviour. To account for overestimation, generally seen in low-prevalence behaviours, an adjusted count technique was applied to the outputs of the classifier. Two generalized linear mixed models were fitted to investigate factors (e.g. age, health) associated with duration of play and number of play instances per day. Our algorithm identified play behaviour with > 94% accuracy when evaluated on the test set with no animals used for training, and 16% overestimation, which was computed based on the predicted number of samples of play versus the number of samples labelled as play on the test set. The instances and duration of play behaviour per day significantly decreased with age and sickness, whilst play behaviour significantly increased during and after weaning. The instances of play also significantly decreased as mean temperature increased. We suggest that the quantification method that we used could be used to detect and monitor other low prevalence behaviours (e.g. social grooming) from location data, including indicators of positive welfare

Second asymptomatic carotid surgery trial (ACST-2): a randomised comparison of carotid artery stenting versus carotid endarterectomy

Background: Among asymptomatic patients with severe carotid artery stenosis but no recent stroke or transient cerebral ischaemia, either carotid artery stenting (CAS) or carotid endarterectomy (CEA) can restore patency and reduce long-term stroke risks. However, from recent national registry data, each option causes about 1% procedural risk of disabling stroke or death. Comparison of their long-term protective effects requires large-scale randomised evidence. Methods: ACST-2 is an international multicentre randomised trial of CAS versus CEA among asymptomatic patients with severe stenosis thought to require intervention, interpreted with all other relevant trials. Patients were eligible if they had severe unilateral or bilateral carotid artery stenosis and both doctor and patient agreed that a carotid procedure should be undertaken, but they were substantially uncertain which one to choose. Patients were randomly allocated to CAS or CEA and followed up at 1 month and then annually, for a mean 5 years. Procedural events were those within 30 days of the intervention. Intention-to-treat analyses are provided. Analyses including procedural hazards use tabular methods. Analyses and meta-analyses of non-procedural strokes use Kaplan-Meier and log-rank methods. The trial is registered with the ISRCTN registry, ISRCTN21144362. Findings: Between Jan 15, 2008, and Dec 31, 2020, 3625 patients in 130 centres were randomly allocated, 1811 to CAS and 1814 to CEA, with good compliance, good medical therapy and a mean 5 years of follow-up. Overall, 1% had disabling stroke or death procedurally (15 allocated to CAS and 18 to CEA) and 2% had non-disabling procedural stroke (48 allocated to CAS and 29 to CEA). Kaplan-Meier estimates of 5-year non-procedural stroke were 2·5% in each group for fatal or disabling stroke, and 5·3% with CAS versus 4·5% with CEA for any stroke (rate ratio [RR] 1·16, 95% CI 0·86–1·57; p=0·33). Combining RRs for any non-procedural stroke in all CAS versus CEA trials, the RR was similar in symptomatic and asymptomatic patients (overall RR 1·11, 95% CI 0·91–1·32; p=0·21). Interpretation: Serious complications are similarly uncommon after competent CAS and CEA, and the long-term effects of these two carotid artery procedures on fatal or disabling stroke are comparable. Funding: UK Medical Research Council and Health Technology Assessment Programme

Insight from an Italian Delphi Consensus on EVAR feasibility outside the instruction for use: the SAFE EVAR Study

BACKGROUND: The SAfety and FEasibility of standard EVAR outside the instruction for use (SAFE-EVAR) Study was designed to define the attitude of Italian vascular surgeons towards the use of standard endovascular repair (EVAR) for infrarenal abdominal aortic aneurysm (AAA) outside the instruction for use (IFU) through a Delphi consensus endorsed by the Italian Society of Vascular and Endovascular Surgery (Societa Italiana di Chirurgia Vascolare ed Endovascolare - SICVE). METHODS: A questionnaire consisting of 26 statements was developed, validated by an 18 -member Advisory Board, and then sent to 600 Italian vascular surgeons. The Delphi process was structured in three subsequent rounds which took place between April and June 2023. In the first two rounds, respondents could indicate one of the following five degrees of agreement: 1) strongly agree; 2) partially agree; 3) neither agree nor disagree; 4) partially disagree; 5) strongly disagree; while in the third round only three different choices were proposed: 1) agree; 2) neither agree nor disagree; 3) disagree. We considered the consensus reached when >70% of respondents agreed on one of the options. After the conclusion of each round, a report describing the percentage distribution of the answers was sent to all the participants. RESULTS: Two -hundred -forty-four (40.6%) Italian Vascular Surgeons agreed to participate the first round of the Delphi Consensus; the second and the third rounds of the Delphi collected 230 responders (94.3% of the first -round responders). Four statements (15.4%) reached a consensus in the first rounds. Among the 22 remaining statements, one more consensus (3.8%) was achieved in the second round. Finally, seven more statements (26.9%) reached a consensus in the simplified last round. Globally, a consensus was reached for almost half of the proposed statements (46.1%). CONCLUSIONS: The relatively low consensus rate obtained in this Delphi seems to confirm the discrepancy between Guideline recommendations and daily clinical practice. The data collected could represent the source for a possible guidelines' revision and the proposal of specific Good Practice Points in all those aspects with only little evidence available

El primer contrato fluvial en Italia y la experiencia del Parque Fluvial del Lura: Objetivos, estrategias, acciones y resultados para lograr formas más resilientes y saludables de habitar los territorios y las ciudades.

La contribución identifica el tema de la crisis climática, reflexionando sobre la relación hombre-medio ambiente en la relación recíproca causa-consecuencia a través de la cual los efectos de la antropización del territorio afectan a la salubridad del medio ambiente y a la calidad de vida. En el diseño arquitectónico reside el cambio de paradigma, de un círculo vicioso a uno virtuoso: el diseño del espacio abierto puede convertirse en un constructor de ciudades y territorios más salubres para mejorar la calidad de vida. El caso de estudio se sitúa en el área metropolitana septentrional de Milán, una región densamente poblada y edificada. Presidiendo su territorio se encuentra el Parque del Valle del Lura, que forma parte del primer Contrato Fluvial italiano activo desde 2004: una herramienta de gobernanza supra administrativa que elige la cuenca fluvial como unidad de referencia para las políticas de reordenación ambiental y paisajística. Un territorio en torno al río denso de fragilidad, donde el elemento de crisis es la forma de los lugares, resultado de una expansión urbana incontrolada que ha modificado el medio natural, fluvial y agrícola, restituyendo un paisaje de fragmentos comprimidos por los márgenes de las aglomeraciones, “espaldas de mundos”: de placas industriales, vallas, aparcamientos, carreteras interrumpidas. Por otro lado, la fragmentación de los espacios agrícolas y naturales genera discontinuidades ecológicas, que se ven amplificadas por las infraestructuras de autopistas y ferrocarriles que atraviesan los paisajes. La contribución investiga las estrategias, acciones y resultados (reforestación, laminación, reconstrucción de hábitats naturales, movilidad sostenible, redefinición de márgenes urbanos) de la experiencia de 20 años del Parque Lura dentro del Contrato Fluvial como participante activo en la restauración de valores y cualidades espaciales, con el fin de contemplar futuras acciones y estrategias para restaurar contextos inciertos, formas nuevas y salubres de habitar territorios y ciudades