132 research outputs found

    Synthesis, Molecular Structure, and 1H NMR Analysis of Bis(tetraphenylcyclopentadienyl)ruthenium(II)

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    Reaction of [Ru(p-cymene)Cl2]2 with K(η5-C5HPh4) in refluxing diglyme yields (η5-C5Ph4)2Ru in ca 50% yield. The complex was not susceptible to oxidation or reduction. (C5HPH4)2Ru crystallizes in the triclinic P1 space group with a = 8.549(4), b = 10.793(4), c = 12.842(5) Å, α = 65.98(3), β = 73.10(3), γ = 83.49(3)° and Z = 1. The least-squares data refined to R(F) = 3.53% and R(wF = 3.82% for the 3952 independent observed reflections with Fo ≥ 5σ(Fo). The metal-centroid distance is 1.832(2) Å and all other bond lengths and angles are similar to other octaphenylmetallocenes. 1H NMR analysis employing 2D J-resolved, COSY and low temperature techniques allowed assignment of all protons in the molecule. The motional processes of the phenyl groups are discussed

    Hybrid kernelised expectation maximisation for Bremsstrahlung SPECT reconstruction in SIRT with 90Y micro-spheres

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    BACKGROUND: Selective internal radiation therapy with Yttrium-90 microspheres is an effective therapy for liver cancer and liver metastases. Yttrium-90 is mainly a high-energy beta particle emitter. These beta particles emit Bremsstrahlung radiation during their interaction with tissue making post-therapy imaging of the radioactivity distribution feasible. Nevertheless, image quality and quantification is difficult due to the continuous energy spectrum which makes resolution modelling, attenuation and scatter estimation challenging and therefore the dosimetry quantification is inaccurate. As a consequence a reconstruction algorithm able to improve resolution could be beneficial. METHODS: In this study, the hybrid kernelised expectation maximisation (HKEM) is used to improve resolution and contrast and reduce noise, in addition a modified HKEM called frozen HKEM (FHKEM) is investigated to further reduce noise. The iterative part of the FHKEM kernel was frozen at the 72nd sub-iteration. When using ordered subsets algorithms the data is divided in smaller subsets and the smallest algorithm iterative step is called sub-iteration. A NEMA phantom with spherical inserts was used for the optimisation and validation of the algorithm, and data from 5 patients treated with Selective internal radiation therapy were used as proof of clinical relevance of the method. RESULTS: The results suggest a maximum improvement of 56% for region of interest mean recovery coefficient at fixed coefficient of variation and better identification of the hot volumes in the NEMA phantom. Similar improvements were achieved with patient data, showing 47% mean value improvement over the gold standard used in hospitals. CONCLUSIONS: Such quantitative improvements could facilitate improved dosimetry calculations with SPECT when treating patients with Selective internal radiation therapy, as well as provide a more visible position of the cancerous lesions in the liver

    Participatory Mapping to Address Neighborhood Level Data Deficiencies for food Security Assessment in Southeastern Virginia, USA

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    Background: Food is not equitably available. Deficiencies and generalizations limit national datasets, food security assessments, and interventions. Additional neighborhood level studies are needed to develop a scalable and transferable process to complement national and internationally comparative data sets with timely, granular, nuanced data. Participatory geographic information systems (PGIS) offer a means to address these issues by digitizing local knowledge. Methods: The objectives of this study were two-fold: (i) identify granular locations missing from food source and risk datasets and (ii) examine the relation between the spatial, socio-economic, and agency contributors to food security. Twenty-nine subject matter experts from three cities in Southeastern Virginia with backgrounds in food distribution, nutrition management, human services, and associated research engaged in a participatory mapping process. Results: Results show that publicly available and other national datasets are not inclusive of non-traditional food sources or updated frequently enough to reflect changes associated with closures, expansion, or new programs. Almost 6 percent of food sources were missing from publicly available and national datasets. Food pantries, community gardens and fridges, farmers markets, child and adult care programs, and meals served in community centers and homeless shelters were not well represented. Over 24 km2 of participant identified need was outside United States Department of Agriculture low income, low access areas. Economic, physical, and social barriers to food security were interconnected with transportation limitations. Recommendations address an international call from development agencies, countries, and world regions for intervention methods that include systemic and generational issues with poverty, incorporate non-traditional spaces into food distribution systems, incentivize or regulate healthy food options in stores, improve educational opportunities, increase data sharing. Conclusions: Leveraging city and regional agency as appropriate to capitalize upon synergistic activities was seen as critical to achieve these goals, particularly for non-traditional partnership building. To address neighborhood scale food security needs in Southeastern Virginia, data collection and assessment should address both environment and utilization issues from consumer and producer perspectives including availability, proximity, accessibility, awareness, affordability, cooking capacity, and preference. The PGIS process utilized to facilitate information sharing about neighborhood level contributors to food insecurity and translate those contributors to intervention strategies through discussion with local subject matter experts and contextualization within larger scale food systems dynamics is transferable

    Triple modality image reconstruction of PET data using SPECT, PET, CT information increases lesion uptake in images of patients treated with radioembolization with [Formula: see text] micro-spheres.

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    PURPOSE: Nuclear medicine imaging modalities like computed tomography (CT), single photon emission CT (SPECT) and positron emission tomography (PET) are employed in the field of theranostics to estimate and plan the dose delivered to tumors and the surrounding tissues and to monitor the effect of the therapy. However, therapeutic radionuclides often provide poor images, which translate to inaccurate treatment planning and inadequate monitoring images. Multimodality information can be exploited in the reconstruction to enhance image quality. Triple modality PET/SPECT/CT scanners are particularly useful in this context due to the easier registration process between images. In this study, we propose to include PET, SPECT and CT information in the reconstruction of PET data. The method is applied to Yttrium-90 ([Formula: see text]Y) data. METHODS: Data from a NEMA phantom filled with [Formula: see text]Y were used for validation. PET, SPECT and CT data from 10 patients treated with Selective Internal Radiation Therapy (SIRT) were used. Different combinations of prior images using the Hybrid kernelized expectation maximization were investigated in terms of VOI activity and noise suppression. RESULTS: Our results show that triple modality PET reconstruction provides significantly higher uptake when compared to the method used as standard in the hospital and OSEM. In particular, using CT-guided SPECT images, as guiding information in the PET reconstruction significantly increases uptake quantification on tumoral lesions. CONCLUSION: This work proposes the first triple modality reconstruction method and demonstrates up to 69% lesion uptake increase over standard methods with SIRT [Formula: see text]Y patient data. Promising results are expected for other radionuclide combination used in theranostic applications using PET and SPECT

    A Genome Wide Survey of SNP Variation Reveals the Genetic Structure of Sheep Breeds

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    The genetic structure of sheep reflects their domestication and subsequent formation into discrete breeds. Understanding genetic structure is essential for achieving genetic improvement through genome-wide association studies, genomic selection and the dissection of quantitative traits. After identifying the first genome-wide set of SNP for sheep, we report on levels of genetic variability both within and between a diverse sample of ovine populations. Then, using cluster analysis and the partitioning of genetic variation, we demonstrate sheep are characterised by weak phylogeographic structure, overlapping genetic similarity and generally low differentiation which is consistent with their short evolutionary history. The degree of population substructure was, however, sufficient to cluster individuals based on geographic origin and known breed history. Specifically, African and Asian populations clustered separately from breeds of European origin sampled from Australia, New Zealand, Europe and North America. Furthermore, we demonstrate the presence of stratification within some, but not all, ovine breeds. The results emphasize that careful documentation of genetic structure will be an essential prerequisite when mapping the genetic basis of complex traits. Furthermore, the identification of a subset of SNP able to assign individuals into broad groupings demonstrates even a small panel of markers may be suitable for applications such as traceability

    Photochemistry of Furyl- and Thienyldiazomethanes: Spectroscopic Characterization of Triplet 3-Thienylcarbene

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    Photolysis (λ \u3e 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N2 at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm–1, |E/hc| = 0.0554 cm–1; |D/hc| = 0.579 cm–1, |E/hc| = 0.0315 cm–1). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding σ orbital between sulfur and the neighboring carbon—an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (λmax = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C5H4S or C5H4O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively)

    Methodological review of NMA bias concepts provides groundwork for the development of a list of concepts for potential inclusion in a new risk of bias tool for network meta-analysis (RoB NMA Tool)

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    INTRODUCTION: Network meta-analyses (NMAs) have gained popularity and grown in number due to their ability to provide estimates of the comparative effectiveness of multiple treatments for the same condition. The aim of this study is to conduct a methodological review to compile a preliminary list of concepts related to bias in NMAs. METHODS AND ANALYSIS: We included papers that present items related to bias, reporting or methodological quality, papers assessing the quality of NMAs, or method papers. We searched MEDLINE, the Cochrane Library and unpublished literature (up to July 2020). We extracted items related to bias in NMAs. An item was excluded if it related to general systematic review quality or bias and was included in currently available tools such as ROBIS or AMSTAR 2. We reworded items, typically structured as questions, into concepts (i.e. general notions). RESULTS: One hundred eighty-one articles were assessed in full text and 58 were included. Of these articles, 12 were tools, checklists or journal standards; 13 were guidance documents for NMAs; 27 were studies related to bias or NMA methods; and 6 were papers assessing the quality of NMAs. These studies yielded 99 items of which the majority related to general systematic review quality and biases and were therefore excluded. The 22 items we included were reworded into concepts specific to bias in NMAs. CONCLUSIONS: A list of 22 concepts was included. This list is not intended to be used to assess biases in NMAs, but to inform the development of items to be included in our tool
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