Advances in polyaromatic and ferrocenyl phosphine chemistry

Condensation of Ph2PCH2OH with a range of polyaromatic substituted secondary amines afforded a new set of “hybrid” phosphine ligands of the type {RCH2N(CH2PPh2)CH2}2 and RCH2N(CH2PPh2)CH2CH3 (R = various planar aromatic groups). The coordination chemistry of these new mono and bidentate ligands towards a range of transition metal centres including Mo(0), Au(I), Rh(I), Ni(II), Pd(II), Pt(II) and Ru(II) was investigated. Ditertiary phosphines of the form {RCH2N(CH2PPh2)CH2}2 were found to be capable of bridging two transition metal centres in addition to forming rare examples of nine–membered cis– and trans– chelate complexes. Single crystal X–ray analysis of these coordination compounds revealed several types of inter– and intramolecular packing interactions (including a C–H···Pt interaction and slipped intermolecular π····π stacking), and also confirmed the rare trans–diphosphine coordination mode. Fluorescent emission measurements have been undertaken on these new tertiary phosphines and their coordination compounds, and these luminescent properties are discussed. A preliminary investigation into the chemosensory behaviour of selected compounds has been undertaken. Using RPCH2OH (RP = Ph2P, Cy2P or AdP = 1,3,5,7,–tetramethyl–2,4,8–trioxa–6– phosphaadamantane) as a versatile precursor, a range of ferrocenyl (Fc) tertiary phosphines have been prepared from a selection of primary and secondary amines. The coordination chemistry of these new mono and bidentate ligands towards several transition metal centres including Cr(0), Mo(0), Au(I), Rh(I), Ru(II), Pd(II) and Pt(II) was investigated. In particular, the previous chemistry was expanded to prepare several new diferrocenyl phosphines of the form {FcCH2N(CH2PR)CH2}2. In a similar manner to their polyaromatic counterparts, these ditertiary phosphines were found to be capable of coordination through both bridging and cis– / trans–chelating modes. Notably, single crystal X–ray analysis was used to confirm the formation of an extremely rare example of a dimeric trans, trans–[Rh(CO)Cl{phosphine}2]2 complex; thought to be the first crystallographically characterised metallacycle containing an Rh2Fe4 arrangement of metal centres. In addition to this {FcCH2N(CH2PR)CH2}2 chemistry, a rare example of a triferrocenyl ditertiary ii phosphine, {FcCH2N(CH2PPh2)CH2}2Fc, was prepared, as well as a macrocyclic ditertiary ferrocenyl phosphine, C10H8Fe(CH2N(CH2PPh2)CH2)2CH2. The coordination chemistry of {FcCH2N(CH2PPh2)CH2}2Fc led to the formation of two unusual examples of pentametallic diphosphine coordination complexes with a Fe3Au2 and Fe3Ru2 arrangement of metal centres. The development of a new phosphinoamine, (Ph2P)2NCH2Fc, and a new ferrocenyl iminophosphine, Ph2PCH(Ph)CH2C(H)NCH2Fc, are also discussed, in addition to a brief investigation of their coordination chemistry. Electrochemical measurements have also been undertaken on these ferrocenyl ligands and their respective coordination compounds (when purity, yield and stability would allow), and their redox chemistry discussed. A series of novel phosphorus(III) containing ligands of the forms (R)N(CH2PPh2)2 and (R)NHCOCH2N(CH2PPh2)2 (R = functionalised planar aromatic or ferrocenyl group) have been prepared. The phosphines were found to readily coordinate several transition metals including Pt(II), Pd(II) and Ru(II) to form a series of new cis– chelate and bridged bimetallic complexes. Analysis by single crystal X–ray diffraction revealed several types of inter- and intramolecular hydrogen bonding within the molecular structures of the phosphines and their coordination compounds, including the formation of several intermolecular 1D chains and the presence of an intramolecular N–H···N bond, which forces a “scorpion–like” conformation

CCN5 modulates the antiproliferative effect of heparin and regulates cell motility in vascular smooth muscle cells

BACKGROUND: Vascular smooth muscle cell (VSMC) hyperplasia plays an important role in both chronic and acute vascular pathologies including atherosclerosis and restenosis. Considerable work has focused on the mechanisms regulating VSMC proliferation and motility. Earlier work in our lab revealed a novel growth arrest-specific (gas) gene induced in VSMC exposed to the antiproliferative agent heparin. This gene is a member of the CCN family and has been given the name CCN5. The objective of the present study is to elucidate the function of CCN5 protein and to explore its mechanism of action in VSMC. RESULTS: Using RNA interference (RNAi), we first demonstrate that CCN5 is required for the antiproliferative effect of heparin in VSMC. We also use this gene knockdown approach to show that CCN5 is an important negative regulator of motility. To explore the mechanism of action of CCN5 on VSMC motility, we use RNAi to demonstrate that knock down of CCN5 up regulates expression of matrix metalloproteinase-2 (MMP-2), an important stimulator of motility in VSMC. In addition, forced expression of CCN5 via adenovirus results in reduced MMP-2 activity, this also corroborates the gene knock down results. Finally, we show that loss of CCN5 expression in VSMC causes changes in VSMC morphology and cytoskeletal organization, including a reduction in the amount and macromolecular assembly of smooth muscle cell α-actin. CONCLUSIONS: This work provides important new insights into the regulation of smooth muscle cell proliferation and motility by CCN5 and may aid the development of therapies for vascular diseases

AGREEMENT AMONG COUNTERMOVEMENT JUMP FORCE-TIME VARIABLES OBTAINED FROM A WIRELESS DUAL FORCE PLATE SYSTEM AND AN INDUSTRY GOLD STANDARD SYSTEM

The purpose of this study was to explore the agreement between a wireless and portable dual force plate system, and an in-ground force plate system, which is an industry gold standard. The countermovement jump (CMJ) was compared across the two systems because it is the most popular force plate test in sports settings. Recreationally active adults (n=20) performed three maximal-effort CMJs on the portable force plates which were placed atop two adjacent in-ground force plates to enable simultaneous collection of raw force-time data (1000 Hz) over five seconds. Popular CMJ force-time variables were analysed for each system using a custom Microsoft Excel spreadsheet using criterion methods. Ordinary least products regression (OLPR) showed no fixed or proportional bias between the force plate systems for all variables. Thus, the portable force plate system may be considered a valid alternative to an industry gold standard for the assessment of CMJ force-time variables

The Use of Mobility Data for Responding to the COVID-19 Pandemic

As the COVID-19 pandemic continues to upend the way people move, work, and gather, governments, businesses, and public health researchers have looked increasingly at mobility data to support pandemic response. This data, assets that describe human location and movement, generally has been collected for purposes directly related to a company's business model, including optimizing the delivery of consumer services, supply chain management or targeting advertisements. However, these call detail records, smartphone-mobility data, vehicle-derived GPS, and other mobility data assets can also be used to study patterns of movement. These patterns of movement have, in turn, been used by organizations to forecast disease spread and inform decisions on how to best manage activity in certain locations.Researchers at The GovLab and Cuebiq, supported by the Open Data Institute, identified 51 notable projects from around the globe launched by public sector and research organizations with companies that use mobility data for these purposes. It curated five projects among this listing that highlight the specific opportunities (and risks) presented by using this asset. Though few of these highlighted projects have provided public outputs that make assessing project success difficult, organizations interviewed considered mobility data to be a useful asset that enabled better public health surveillance, supported existing decision-making processes, or otherwise allowed groups to achieve their research goals.The report below summarizes some of the major points identified in those case studies. While acknowledging that location data can be a highly sensitive data type that can facilitate surveillance or expose data subjects if used carelessly, it finds mobility data can support research and inform decisions when applied toward narrowly defined research questions through frameworks that acknowledge and proactively mitigate risk. These frameworks can vary based on the individual circumstances facing data users, suppliers, and subjects. However, there are a few conditions that can enable users and suppliers to promote publicly beneficial and responsible data use and overcome the serious obstacles facing them.For data users (governments and research institutions), functional access to real-time and contextually relevant data can support research goals, even though a lack of data science competencies and both short and long-term funding sources represent major obstacles for this goal. Data suppliers (largely companies), meanwhile, need governance structures and mechanisms that facilitate responsible re-use, including data re-use agreements that define who, what, where, and when, and under what conditions data can be shared. A lack of regulatory clarity and the absence of universal governance and privacy standards have impeded effective and responsible dissemination of mobility for research and humanitarian purposes. Finally, for both data users and suppliers, we note that collaborative research networks that allow organizations to seek out and provide data can serve as enablers of project success by facilitating exchange of methods and resources, and closing the gap between research and practice.Based on these findings, we recommend the development of clear governance and privacy frameworks, increased capacity building around data use within the public sector, and more regular convenings of ecosystem stakeholders (including the public and data subjects) to broaden collaborative networks. We also propose solutions towards making the responsible use of mobility data more sustainable for longterm impact beyond the current pandemic. A failure to develop regulatory and governance frameworks that can responsibly manage mobility data could lead to a regression to the ad hoc and uncoordinated approaches that previously defined mobility data applications. It could also lead to disparate standards about organizations' responsibilities to the public

The role of the international cocoa germplasm database and the international cocoa quarantine centre in information management and distribution of cocoa genetic resources

A range of physiological parameters (canopy light transmission, canopy shape, leaf size, flowering and flushing intensity) were measured from the International Clone Trial, typically over the course of two years. Data were collected from six locations, these being: Brazil, Ecuador, Trinidad, Venezuela, Côte d’Ivoire and Ghana. Canopy shape varied significantly between clones, although it showed little variation between locations. Genotypic variation in leaf size was differentially affected by the growth location; such differences appeared to underlie a genotype by environment interaction in relation to canopy light transmission. Flushing data were recorded at monthly intervals over the course of a year. Within each location, a significant interaction was observed between genotype and time of year, suggesting that some genotypes respond to a greater extent than others to environmental stimuli. A similar interaction was observed for flowering data, where significant correlations were found between flowering intensity and temperature in Brazil and flowering intensity and rainfall in Côte d’Ivoire. The results demonstrate the need for local evaluation of cocoa clones and also suggest that the management practices for particular planting material may need to be fine-tuned to the location in which they are cultivated

Mid-infrared Selection of Active Galactic Nuclei with the Wide-Field Infrared Survey Explorer. I. Characterizing WISE-selected Active Galactic Nuclei in COSMOS

The Wide-field Infrared Survey Explorer (WISE) is an extremely capable and efficient black hole finder. We present a simple mid-infrared color criterion, W1 – W2 ≥ 0.8 (i.e., [3.4]–[4.6] ≥0.8, Vega), which identifies 61.9 ± 5.4 active galactic nucleus (AGN) candidates per deg^2 to a depth of W2 ~ 15.0. This implies a much larger census of luminous AGNs than found by typical wide-area surveys, attributable to the fact that mid-infrared selection identifies both unobscured (type 1) and obscured (type 2) AGNs. Optical and soft X-ray surveys alone are highly biased toward only unobscured AGNs, while this simple WISE selection likely identifies even heavily obscured, Compton-thick AGNs. Using deep, public data in the COSMOS field, we explore the properties of WISE-selected AGN candidates. At the mid-infrared depth considered, 160 μJy at 4.6 μm, this simple criterion identifies 78% of Spitzer mid-infrared AGN candidates according to the criteria of Stern et al. and the reliability is 95%. We explore the demographics, multiwavelength properties and redshift distribution of WISE-selected AGN candidates in the COSMOS field

Monitoring the US ATLAS Network Infrastructure with perfSONAR-PS

Global scientific collaborations, such as ATLAS, continue to push the network requirements envelope. Data movement in this collaboration is routinely including the regular exchange of petabytes of datasets between the collection and analysis facilities in the coming years. These requirements place a high emphasis on networks functioning at peak efficiency and availability; the lack thereof could mean critical delays in the overall scientific progress of distributed data-intensive experiments like ATLAS. Network operations staff routinely must deal with problems deep in the infrastructure; this may be as benign as replacing a failing piece of equipment, or as complex as dealing with a multi-domain path that is experiencing data loss. In either case, it is crucial that effective monitoring and performance analysis tools are available to ease the burden of management. We will report on our experiences deploying and using the perfSONAR-PS Performance Toolkit at ATLAS sites in the United States. This software creates a dedicated monitoring server, capable of collecting and performing a wide range of passive and active network measurements. Each independent instance is managed locally, but able to federate on a global scale; enabling a full view of the network infrastructure that spans domain boundaries. This information, available through web service interfaces, can easily be retrieved to create customized applications. The US ATLAS collaboration has developed a centralized “dashboard” offering network administrators, users, and decision makers the ability to see the performance of the network at a glance. The dashboard framework includes the ability to notify users (alarm) when problems are found, thus allowing rapid response to potential problems and making perfSONAR-PS crucial to the operation of our distributed computing infrastructure.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/98635/1/1742-6596_396_4_042038.pd

Deep Hubble Space Telescope Imaging of IC 1613 II. The Star Formation History

We present deep HST WFPC2 imaging of the Local Group dwarf irregular galaxy IC 1613. The photometry is the deepest to date for an isolated dwarf irregular galaxy. The resulting color-magnitude diagram (CMD) is analyzed using three different methods to derive a star formation history (SFH). All three find an enhanced star formation rate (SFR), from 3 to 6 Gyr ago, and similar age-metallicity relationships (AMR). A comparison of the newly observed outer field with an earlier studied central field of IC 1613 shows that the SFR in the outer field has been significantly depressed during the last Gyr. This implies that the optical scale length of the galaxy has been decreasing with time and that comparison of galaxies at intermediate redshift with present day galaxies should take this effect into account. We find strong similarities between IC 1613 and the more distant Milky Way dSph companions in that all are dominated by star formation at intermediate ages. In particular, the SFH and AMR for IC 1613 and Leo I are indistinguishable. This implies that dIrr galaxies cannot be distinguished from dSphs by their intermediate age stellar populations. This type of a SFH may also be evidence for slower or suppressed early star formation in dwarf galaxies due to photoionization after the reionization of the universe by background radiation. Assuming that IC 1613 is typical of a dIrr evolving in isolation, since most of the star formation occurs at intermediate ages, these dwarf systems cannot be responsible for the fast chemical enrichment of the IGM which is seen at high redshift. There is no evidence for any large amplitude bursts of star formation in IC 1613, and we find it highly unlikely that analogs of IC 1613 have contributed to the excess of faint blue galaxies in existing galaxy redshift surveys.Comment: 32 pages, including 1 table and 17 figures, accepted for publication in the Astrophysical Journal October 10, 2003 issu

The Validity of Hawkin Dynamics Wireless Dual Force Plates for Measuring Countermovement Jump and Drop Jump Variables

Force plate testing is becoming more commonplace in sport due to the advent of commercially available, portable, and affordable force plate systems (i.e., hardware and software). Following the validation of the Hawkin Dynamics Inc. (HD) proprietary software in recent literature, the aim of this study was to determine the concurrent validity of the HD wireless dual force plate hardware for assessing vertical jumps. During a single testing session, the HD force plates were placed directly atop two adjacent Advanced Mechanical Technology Inc. in-ground force plates (the “gold standard”) to simultaneously collect vertical ground reaction forces produced by 20 participants (27 ± 6 years, 85 ± 14 kg, 176.5 ± 9.23 cm) during the countermovement jump (CMJ) and drop jump (DJ) tests (1000 Hz). Agreement between force plate systems was determined via ordinary least products regression using bootstrapped 95% confidence intervals. No bias was present between the two force plate systems for any of the CMJ and DJ variables, except DJ peak braking force (proportional bias) and DJ peak braking power (fixed and proportional bias). The HD system may be considered a valid alternative to the industry gold standard for assessing vertical jumps because fixed or proportional bias was identified for none of the CMJ variables (n = 17) and only 2 out of 18 DJ variables

Protocol for a cluster-randomised non-inferiority trial of one versus two doses of ivermectin for the control of scabies using a mass drug administration strategy (the RISE study).

INTRODUCTION: Scabies is a significant contributor to global morbidity, affecting approximately 200 million people at any time. Scabies is endemic in many resource-limited tropical settings. Bacterial skin infection (impetigo) frequently complicates scabies infestation in these settings. Community-wide ivermectin-based mass drug administration (MDA) is an effective control strategy for scabies in island settings, with a single round of MDA reducing population prevalence by around 90%. However, current two-dose regimens present a number of barriers to programmatic MDA implementation. We designed the Regimens of Ivermectin for Scabies Elimination (RISE) trial to investigate whether one-dose MDA may be as effective as two-dose MDA in controlling scabies in high-prevalence settings. METHODS AND ANALYSIS: RISE is a cluster-randomised non-inferiority trial. The study will be conducted in 20 isolated villages in Western Province of Solomon Islands where population prevalence of scabies is approximately 20%. Villages will be randomly allocated to receive either one dose or two doses of ivermectin-based MDA in a 1:1 ratio. The primary objective of the study is to determine if ivermectin-based MDA with one dose is as effective as MDA with two doses in reducing the prevalence of scabies after 12 months. Secondary objectives include the effect of ivermectin-based MDA on impetigo prevalence after 12 and 24 months, the prevalence of scabies at 24 months after the intervention, the impact on presentation to health facilities with scabies and impetigo, and the safety of one-dose and two-dose MDA. ETHICS AND DISSEMINATION: This trial has been approved by the ethics review committees of the Solomon Islands and the Royal Children's Hospital, Australia. Results will be disseminated in peer-reviewed publications and in meetings with the Solomon Islands Ministry of Health and Medical Services and participating communities. TRIAL REGISTRATION DETAILS: Australian New Zealand Clinical Trials Registry: ACTRN12618001086257. Date registered: 28 June 2018