Oxidative Addition To Platinum(ii) Complexes

This thesis describes the oxidative addition of alcohols, water and organic halides to dimethyl(2,2-bipyridine)platinum(II) (complex (I)) and to dimethyl(1,10-phenanthroline)platinum(II) (complex (II)). The work has involved characterising the reaction products and investigating the mechanism of oxidative addition. Up to now very little mechanistic work has been done for oxidative addition at platinum(II) centres.;Complexes (I) and (II) react with methanol, ethanol and isopropanol to produce the first series of platinum(IV) alkoxides of general formula {lcub}PtMe(,2)(OR)(N N)H(,2)O{rcub}(\u27+){lcub}OH{rcub}(\u27-) (N N = bipy or phen; R = Me, Et, (\u27i)Pr). Characterisation was achieved by (\u271)H nmr, (\u2713)C nmr and elemental analysis. In an analogous reaction with water the product was a platinum(IV) hydroxo complex.;Primary organic halides reacted cleanly with complex (II) to produce complexes of general formula {lcub}PtXMe(,2)(R)(phen){rcub} (X = I or Br; R = Me, Et, (\u27n)Pr, (\u27n)Bu). The reactions proceed via an S(,N)2 mechanism.;The reaction of complex (II) with methylene dihalides is believed to proceed via the intermediacy of free-radicals. The reaction of CH(,2)X(,2) (X = Cl, Br or I) with (II) produced a mixture of cis- and trans-isomers of general formula {lcub}PtXMe(,2)(CH(,2)X)(phen){rcub}. Complex (II) reacted with CH(,2)ClI producing a mixture of platinum(IV) complexes, which involved halogen scrambling.;The reaction of X(CH(,2))(,2)X (X = I or Br) with (II) is thought to proceed via competing radical chain and radical non-chain mechanisms. The novel binuclear complexes {lcub}Pt(,2)X(,2)Me(,4){lcub}(CH(,2))(,2){rcub}(phen)(,2){rcub} were isolated from these reactions.;The reaction of (II) with an excess of the (alpha),(omega)-diiodoalkanes I(CH(,2))(,n)I (n = 3-5) produced mononuclear complexes of general formula {lcub}PtIMe(,2){lcub}(CH(,2))(,n)I{rcub}(phen){rcub}. The reaction proceeds via an S(,N)2 mechanism. These mononuclear complexes reacted further with (II), also via an S(,N)2 mechanism to produce the binuclear bridging polymethylene complexes, {lcub}Pt(,2)I(,2)Me(,4){lcub}(CH(,2))(,n){rcub}(phen){rcub}. The rate-constants for these reactions could be measured and indicate a neighbouring atom effect for the reaction of the complexes, {lcub}PtIMe(,2){lcub}(CH(,2))(,n)I{rcub}(phen){rcub}, with (II). In deoxygenated solvent isopropyl iodide reacted with (II) to form {lcub}PtIMe(,2)((\u27i)Pr)(phen){rcub}. However, in the presence of dioxygen the major product was {lcub}PtIMe(,2)((\u27i)PROO)(phen){rcub}. This is the first platinum(IV)peroxo complex to be isolated and a single crystal x-ray structure was performed for this complex. . . . (Author\u27s abstract exceeds stipulated maximum length. Discontinued here with permission of author.) UM

Serogroups of Dichelobacter nodosus, the cause of footrot in sheep, are randomly distributed across England

We present the largest and most representative study of the serological diversity of Dichelobacter nodosus in England. D. nodosus causes footrot and is one of the top five globally important diseases of sheep. The commercial vaccine, containing nine serogroups, has low efficacy compared with bivalent vaccines. Our aim was to investigate the prevalence and distribution of serogroups of D. nodosus in England to elucidate whether a bivalent vaccine could protect the national flock. Farmers from 164 flocks submitted eight interdigital swabs from eight, preferably diseased, sheep. All serogroups, A–I, were detected by PCR in 687/1150 D. nodosus positive swabs, with a prevalence of 2.6–69.3% of positive swabs per serogroup. There was a median of two serogroups per flock (range 0–6). Serogroups were randomly distributed between, but clustered within, flocks, with 50 combinations of serogroups across flocks. H and B were the most prevalent serogroups, present in > 60% of flocks separately but in only 27% flocks together. Consequently, a bivalent vaccine targeting these two serogroups would protect 27% of flocks fully (if only H and B present) and partially, if more serogroups were present in the flock. We conclude that one bivalent vaccine would not protect the national flock against footrot and, with 50 combinations of serogroups in flocks, flock-specific vaccines are necessary

Experimental Verification of Source Temperature Modulation Via a Thermal Switch in Thermal Energy Harvesting

This paper provides a description of research seeking to experimentally verify the effectiveness of a thermal switch used in series with TE devices for waste heat recovery for constant and variable source heat input and for variable source thermal capacitance (mass). Using an experimental set-up comprised serially of a fixed heat source, a variable thermal resistance air gap serving as a thermal switch, a thermoelectric device and a heat sink, the time-averaged power output to power input ratios improved up to 15% and 30% respectively for constant and variable heat input in certain design space conditions. The experimental results, as supported by model predictions, suggest that the thermal capacitance of the heat source must be greater than the thermal capacitance of the TE device in order for thermal switching to improve the time-averaged power output to power input ratios of waste heat recovery systems. The results have direct application to aircraft energy harvesting

Long-Term Outcomes in Anterior Cruciate Ligament Reconstruction: A Systematic Review of Patellar Tendon Versus Hamstring Autografts.

BACKGROUND: Much controversy still exists surrounding graft choice in anterior cruciate ligament (ACL) reconstruction. Over the past decade, an increase in comparative studies with longer follow-up has enhanced our understanding of current graft options and outcomes. PURPOSE: To describe the long-term comparative outcomes of ACL reconstruction with autograft bone-patellar tendon-bone (BPTB) versus autograft hamstring (HS) ACL reconstruction with regard to clinical and radiographic outcomes. STUDY DESIGN: Systematic review; Level of evidence, 2. METHODS: A search of the PubMed, MEDLINE, Cochrane, and Scopus databases was performed to identify studies in the English language with outcome data comparing ACL reconstruction utilizing autograft BPTB and autograft HS; only studies with a minimum 5-year follow-up were included. Outcome data included failure and complications, manual and instrumented laxity, patient-reported outcomes, and radiographic risk of osteoarthritis. RESULTS: Twelve studies with a total of 953 patients met the inclusion criteria. Of these studies, 8 were level 1 evidence and 2 were level 2. Mean follow-up was 8.96 years (range, 5-15.3 years). No differences in graft failure or manual or instrumented laxity were seen in any studies. Lower clinical outcomes scores and greater motion loss were seen in BPTB patients in 1 and 2 studies, respectively. Two of 4 studies reporting on anterior knee pain, and 3 of 7 that recorded kneeling pain found it more frequently among BPTB patients. One study found significantly increased reoperation rates in HS patients, while another found a similar result in BPTB, and 1 study reported a significant increase in contralateral ACL tears in BPTB patients. Three of 5 studies reporting on radiographic evidence of osteoarthritis noted significantly increased rates in BPTB patients. CONCLUSION: This systematic review comparing long-term outcomes after ACL reconstruction with either autograft BPTB or autograft HS suggests no significant differences in manual/instrumented laxity and graft failures between graft types. An increase in long-term anterior knee pain, kneeling pain, and higher rates of osteoarthritis were noted with BPTB graft use

“Hobocops”: Undercover Policing’s Deceptive Encounters

Policing cultures have reflected a conservative mindedness, particularly when directed toward street-involved, unhoused persons. Yet alongside an increase in urban poverty across Canada, public police today have taken up a puzzling, disturbing affinity with the identity of homelessness. We explore public police use of an undercover technique called “hobocops”. As part of these operations, public police disguise themselves as homeless people holding cardboard signs at busy motor traffic intersections as a way of regulating distracted driving. We explore these practices as encounters between the increasingly everyday activities of covert policing, urban governance, and a sociological account of police engaging in identity co-optation. Detailing how hobocop operations have unfolded in Canada, we contribute to the literature on covert policing by focusing on the operatives of these deceptive encounters rather than the targets. Drawing on the results of freedom of information requests and media reporting, we suggest that hobocop operations are undertaken in part because of police officer enjoyment of enacting the hobo identity. Applying literature on deception in policing and on the degradation of homeless persons, we reflect on the implications of these deceptive encounters for public policing and literature on criminal justice practices

Identification of proteins from the secretory/excretory products (SEPs) of the branchiuran ectoparasite Argulus foliaceus (Linnaeus, 1758) reveals unique secreted proteins amongst haematophagous ecdysozoa

Background It is hypothesised that being a blood-feeding ectoparasite, Argulus foliaceus (Linnaeus, 1758), uses similar mechanisms for digestion and host immune evasion to those used by other haematophagous ecdysozoa, including caligid copepods (e.g. sea louse). We recently described and characterised glands associated with the feeding appendages of A. foliaceus using histological techniques. The work described in the present study is the first undertaken with the objective of identifying and partially characterising the components secreted from these glands using a proteomic approach. Methods Argulus foliaceus parasites were sampled from the skin of rainbow trout (Oncorhynchus mykiss), from Loch Fad on the Isle of Bute, Scotland, UK. The proteins from A. foliaceus secretory/excretory products (SEPs) were collected from the supernatant of artificial freshwater conditioned with active adult parasites (n = 5–9 per ml; n = 560 total). Proteins within the SEPs were identified and characterised using LC-ESI-MS/MS analysis. Data are available via ProteomeXchange with identifier PXD016226. Results Data mining of a protein database translated from an A. foliaceus dataset using ProteinScape allowed identification of 27 predicted protein sequences from the A. foliaceus SEPs, each protein matching the criteria of 2 peptides with at least 4 contiguous amino acids. Nine proteins had no matching sequence through OmicsBox (Blast2GO) analysis searches suggesting that Argulus spp. may additionally have unique proteins present in their SEPs. SignalP 5.0 software, identified 13 proteins with a signal sequence suggestive of signal peptides and supportive of secreted proteins being identified. Notably, the functional characteristics of identified A. foliaceus proteins/domains have also been described from the salivary glands and saliva of other blood-feeding arthropods such as ticks. Identified proteins included: transporters, peroxidases, metalloproteases, proteases and serine protease inhibitors which are known to play roles in parasite immune evasion/induction (e.g. astacin), immunomodulation (e.g. serpin) and digestion (e.g. trypsin). Conclusions To our knowledge, the present study represents the first proteomic analysis undertaken for SEPs from any branchiuran fish louse. Here we reveal possible functional roles of A. foliaceus SEPs in digestion and immunomodulation, with a number of protein families shared with other haematophagous ectoparasites. A number of apparently unique secreted proteins were identified compared to other haematophagous ecdysozoa

Enriching the fan experience in a smart stadium using internet of things technologies

Rapid urbanization has brought about an influx of people to cities, tipping the scale between urban and rural living. Population predictions estimate that 64% of the global population will reside in cities by 2050. To meet the growing resource needs, improve management, reduce complexities, and eliminate unnecessary costs while enhancing the quality of life of citizens, cities are increasingly exploring open innovation frameworks and smart city initiatives that target priority areas including transportation, sustainability, and security. The size and heterogeneity of urban centers impede progress of technological innovations for smart cities. We propose a Smart Stadium as a living laboratory to balance both size and heterogeneity so that smart city solutions and Internet of Things (IoT) technologies may be deployed and tested within an environment small enough to practically trial but large and diverse enough to evaluate scalability and efficacy. The Smart Stadium for Smart Living initiative brings together multiple institutions and partners including Arizona State University (ASU), Dublin City University (DCU), Intel Corporation, and Gaelic Athletic Association (GAA), to turn ASU's Sun Devil Stadium and Ireland's Croke Park Stadium into twinned smart stadia to investigate IoT and smart city technologies and applications