Ruthenium polypyridyl complexes with long aliphatic chains; photophysics, interfacial assembly and cell imaging

A series of novel Ruthenium polypyridyl complexes [Ru(dpp)2(x-ATAP)](PF6)2 were synthesised and their photophysical and electrochemical properties are reported on, where x-ATAP is either 5-Amido-1,10-phenanthroline-(6-acetylthio-hexanyl), 5-Amido-1,10-phenanthroline-(8-acetylthio-octanyl), 5-Amido-1,10-phenanthroline-(11-acetylthio-undecanyl) or 5-Amido-1,10-phenanthroline-(16-acetylthio-hexadecanyl). These complexes exhibit bright emission. They are capable of self assembly on metallic surfaces. Furthermore, this series of complexes are capable of forming bilayer vesicle structures in aqueous conditions. Chapter 3 describes the synthesis, photophysics and solution phase electrochemistry of these complexes. The solvent dependence of the luminescence properties is also addressed along with the formation of bilayer vesicles of these compounds in aqueous conditions. In chapter 4 self assembled monolayers of the Ru(dpp)2(x-ATAP)](PF6)2 complexes were formed on platinum electrodes and these monolayers were characterized electrochemically. These monolayers were found to be somewhat unstable when analysed electrochemically even when backfilled with an appropriate length alkanethiol. Attempts to study the distance dependence of electron transfer reveal that these complexes when functionalized on metal surfaces lie flat on the surface as opposed to the ruthenium headgroup being raised above the surface. The photophysical properties of these monolayers on gold and platinum electrodes and gold nanoparticles are also reported. Despite the close proximity of the headgroup to the metal surface the monolayers remain luminescent and exhibit large SERS enhancement when absorbed on aggregated gold nanoparticle clusters. Chapter 5 explores the interactions of the Ru(dpp)2(x-ATAP)](PF6)2 complexes with monoclonal cells and their suitability as luminescence cell imaging probes. A CHO cell line (Chinese hamster ovary cell) were stained with the Ru(dpp)2(x-ATAP)](PF6)2. This series of complexes was capable of crossing the cell membrane barrier and localizing in discrete compartments of the cell. The stained cell line was imaged by FLIM (fluorescence lifetime imaging microscopy) and 3D z-stacked images of the cell were constructed. It was found that there was an alkyl chain length dependence on the localization of these complexes within the cell. Complexes with short alkyl chains stained throughout the cytoplasm and nucleus while the complexes with longer alkyl chains remain localized in endosomes. Finally chapter 6 explores a novel ruthenium(II) bis-terpyridyl type complex, [RuII(LKet)2].(PF6)2. This complex was characterized photophysically and electrochemically. By extending the structure of the 2,2';6',2"-terpyridine (tpy) ligands with carbonyl bridging units the ruthenium the [RuII(LKet)2].(PF6)2 complex cage structure is much closer to perfect octahedral configuration compared to [RuII(tpy)2]2+. The photophysical performance in ambient conditions of [RuII(LKet)2].(PF6)2 is massively increased compared to [RuII(tpy)2]2+ or similar complexes and this complex displays the longest luminescence lifetime of any ruthenium complex at 298 K and in aerated conditions to our knowledge. The long term aims of this work is to modify this complex with a long chain alkane or peptide for cell imaging purposes

Two-dimensional Stokes flow driven by elliptical paddles

A fast and accurate numerical technique is developed for solving the biharmonic equation in a multiply connected domain, in two dimensions. We apply the technique to the computation of slow viscous flow (Stokes flow) driven by multiple stirring rods. Previously, the technique has been restricted to stirring rods of circular cross section; we show here how the prior method fails for noncircular rods and how it may be adapted to accommodate general rod cross sections, provided only that for each there exists a conformal mapping to a circle. Corresponding simulations of the flow are described, and their stirring properties and energy requirements are discussed briefly. In particular the method allows an accurate calculation of the flow when flat paddles are used to stir a fluid chaotically

The Jewish hellenist and the medieval Jewish philosopher: A comparison of philo of Alexandria and Saadia Ben Joseph

Two of Judaism's greatest philosophers were Philo of Alexandria (c. 20BCE-50CE) and Saadia ben Joseph (882-942). As the first, who in­ fluenced the development of Christian dogma, is the only Jewish Hellenistic philosopher from whom a body of work has survived, and the second can be considered the father of medieval Jewish philosophy, a comparison is of import

A Control-Centric Benchmark for Video Prediction

Video is a promising source of knowledge for embodied agents to learn models of the world's dynamics. Large deep networks have become increasingly effective at modeling complex video data in a self-supervised manner, as evaluated by metrics based on human perceptual similarity or pixel-wise comparison. However, it remains unclear whether current metrics are accurate indicators of performance on downstream tasks. We find empirically that for planning robotic manipulation, existing metrics can be unreliable at predicting execution success. To address this, we propose a benchmark for action-conditioned video prediction in the form of a control benchmark that evaluates a given model for simulated robotic manipulation through sampling-based planning. Our benchmark, Video Prediction for Visual Planning ($VP^2$), includes simulated environments with 11 task categories and 310 task instance definitions, a full planning implementation, and training datasets containing scripted interaction trajectories for each task category. A central design goal of our benchmark is to expose a simple interface -- a single forward prediction call -- so it is straightforward to evaluate almost any action-conditioned video prediction model. We then leverage our benchmark to study the effects of scaling model size, quantity of training data, and model ensembling by analyzing five highly-performant video prediction models, finding that while scale can improve perceptual quality when modeling visually diverse settings, other attributes such as uncertainty awareness can also aid planning performance.Comment: ICLR 202

The eyes have it?-intra- and inter-observer reproducibility of the PD-L1 companion diagnostic assay

No abstract available

Sinapinic and protocatechuic acids found in rapeseed: isolation, characterisation and potential benefits for human health as functional food ingredients

peer-reviewedRapeseed is one of the world’s major oilseeds, and rapeseed oil is produced by pressing of the seeds. This process results in the production of a low-economic-value by-product, rapeseed meal, which is commonly used as animal feed. Rapeseed meal is rich in bioactive phenolic compounds, including sinapinic acid (SA) and protocatechuic acid (PCA). Isolation of these bioactive compounds from a by-product of rapeseed oil production is largely in agreement with the current concept of the circular economy and total utilisation of crop harvest using a biorefinery approach. In this review, current information concerning traditional and novel methods to isolate phenolic compounds – including SA and PCA – from rapeseed meal, along with in vitro and in vivo studies concerning the bioactivity of SA and PCA and their associated health effects, is collated. These health effects include anti-inflammatory, anti-cancer, anti-diabetes activities, along with histone deacetylase inhibition and protective cardiovascular, neurological and hepatic effects. The traditional extraction methods include use of solvents and/or enzymes. However, a need for simpler, more efficient methodologies has led to the development of novel extraction processes, including microwave-assisted, ultrasound-assisted, pulsed electric field and high-voltage electrical discharge extraction processes

Development of a scoring method to identify important areas of plant diversity in Ireland

peer-reviewedIn the face of accelerating biodiversity loss it is more important than ever to identify important areas of biodiversity and target limited resources for conservation. We developed a method to identify areas of important plant diversity using known species’ distributions and evaluations of the species importance. We collated distribution records of vascular plants and developed a scoring method of spatial prioritisation to assign conservation value to the island of Ireland at the hectad scale (10 km × 10 km) and at the tetrad scale (2 km × 2 km) for two counties where sufficient data were available. Each plant species was assigned a species conservation value based on both its conservation status and distribution in Ireland. For each cell, the species conservation values within the cell were summed, thereby differentiating between areas of high and low conservation value across the landscape. Areas with high conservation value represent the most important areas for plant conservation. The protected area cover and the number of species present in these important areas were also examined by first defining threshold values using two different criteria. Species representation was high in the important areas; the identified important areas of plant diversity maintained high representation of species of conservation concern and achieved high species representation overall, requiring a low number of sites (<8%) to do so. The coincidence of protected areas and important areas for plant diversity was found to be low and while some important areas of plant diversity might benefit from the general protection afforded by these areas, our research highlights the need for conservation outside of protected areas

Emotions in telephone calls to emergency medical services involving out-of-hospital cardiac arrest: A scoping review

Aims: The purpose of this scoping review was to identify and synthesise existing research evidence on emotions in the context of emergency phone calls to emergency medical services (EMS) involving out-of-hospital cardiac arrest (OHCA). The specific objectives were to identify studies that (1) described emotions during emergency OHCA calls; (2) specified an instrument or method for measuring/assessing emotions; and (3) examined the relationship between emotions and call outcomes or patient outcomes. Methods/Data sources: Five databases were searched on 18 November 2021: Medline, Embase, PsycInfo, CINAHL, and the Cochrane Review Database. Included studies required the following three concepts to be addressed: emotions in the context of EMS calls that involved OHCA. Calls also needed to be made by a ‘second-party’ caller; and each study needed to address at least one of the three specific objectives, as outlined above. The review was conducted in accordance with the Joanna Briggs Institute guidelines for evidence synthesis for scoping reviews. Results: Thirteen eligible studies were included for synthesis. All studies met Objective 1; six studies met Objective 2; and seven met Objective 3. One study reported patient fatality due to heightened emotions and ensuing ineffective communications between callers and call-takers. Conclusion: The review highlights a significant gap in the evidence base of emotions in emergency OHCA-related calls, and the need for a more comprehensive and effective method in assessing and measuring emotions in this context. Relationships between emotions (their expressions and perceptions) and call outcomes (including patient outcomes) also need more rigorous investigation