21 research outputs found

    Antiphospholipid autoantibodies as blood biomarkers for detection of early stage Alzheimer's disease

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    A robust blood biomarker is urgently needed to facilitate early prognosis for those at risk for Alzheimer's disease (AD). Redox reactive autoantibodies (R-RAAs) represent a novel family of antibodies detectable only after exposure of cerebrospinal fluid (CSF), serum, plasma or immunoglobulin fractions to oxidizing agents. We have previously reported that R-RAA antiphospholipid antibodies (aPLs) are significantly decreased in the CSF and serum of AD patients compared to healthy controls (HCs). These studies were extended to measure R-RAA aPL in serum samples obtained from Alzheimer's Disease Neuroimaging Initiative (ADNI). Serum samples from the ADNI-1 diagnostic groups from participants with mild cognitive impairment (MCI), AD and HCs were blinded for diagnosis and analyzed for R-RAA aPL by ELISA. Demographics, cognitive data at baseline and yearly follow-up were subsequently provided by ADNI after posting assay data. As observed in CSF, R-RAA aPL in sera from the AD diagnostic group were significantly reduced compared to HC. However, the sera from the MCI population contained significantly elevated R-RAA aPL activity relative to AD patient and/or HC sera. The data presented in this study indicate that R-RAA aPL show promise as a blood biomarker for detection of early AD, and warrant replication in a larger sample. Longitudinal testing of an individual for increases in R-RAA aPL over a previously established baseline may serve as a useful early sero-epidemiologic blood biomarker for individuals at risk for developing dementia of the Alzheimer's type

    AndrewAnnex/SpiceyPy: SpiceyPy-1.1.0.dev0

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    draft release of 1.1.0.dev0, in preparation of v1.1.

    AndrewAnnex/SpiceyPy: SpiceyPy 1.1.1

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    Last release to feature N65 Spice, future releases will target N66 Added added python3.6 builds Fixed fixed formatting on changelog fixed issues with rtd builds Changed version updated converted all downloads to use http

    An Ion‐Pairing Approach to Stereoselective Metal‐Free Ring‐Opening Metathesis Polymerization

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    Stereochemistry can have a profound impact on polymer and materials properties. Unfortunately, straightforward methods for realizing high levels of stereocontrolled polymerizations are often challenging to achieve. In a departure from traditional metal‐mediated ring‐opening metathesis polymerization (ROMP), we discovered a remarkably simple method for controlling alkene stereochemistry in photoredox mediated metal‐free ROMP. Ion‐pairing, initiator sterics, and solvation effects each had profound impact on the stereochemistry of polynorbornene (PNB). Simple modifications to the reaction conditions produced PNB with trans alkene content of 25 to >98 %. High cis content was obtained from relatively larger counterions, toluene as solvent, low temperatures (−78 °C), and initiators with low Charton values. Conversely, smaller counterions, dichloromethane as solvent, and enol ethers with higher Charton values enabled production of PNB with high trans content. Data from a combined experimental and computational investigation are consistent with the stereocontrolling step of the radical cationic mechanism proceeding under thermodynamic control.Stereoselective ring‐opening metathesis polymerization is achieved by non‐covalent interactions, such as ion‐pairing, initiator sterics and solvation effects, in a metal‐free condition.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/168301/1/anie202016393.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/168301/2/anie202016393_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/168301/3/anie202016393-sup-0001-misc_information.pd

    An Ion‐Pairing Approach to Stereoselective Metal‐Free Ring‐Opening Metathesis Polymerization

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    Stereochemistry can have a profound impact on polymer and materials properties. Unfortunately, straightforward methods for realizing high levels of stereocontrolled polymerizations are often challenging to achieve. In a departure from traditional metal‐mediated ring‐opening metathesis polymerization (ROMP), we discovered a remarkably simple method for controlling alkene stereochemistry in photoredox mediated metal‐free ROMP. Ion‐pairing, initiator sterics, and solvation effects each had profound impact on the stereochemistry of polynorbornene (PNB). Simple modifications to the reaction conditions produced PNB with trans alkene content of 25 to >98 %. High cis content was obtained from relatively larger counterions, toluene as solvent, low temperatures (−78 °C), and initiators with low Charton values. Conversely, smaller counterions, dichloromethane as solvent, and enol ethers with higher Charton values enabled production of PNB with high trans content. Data from a combined experimental and computational investigation are consistent with the stereocontrolling step of the radical cationic mechanism proceeding under thermodynamic control.Stereoselective ring‐opening metathesis polymerization is achieved by non‐covalent interactions, such as ion‐pairing, initiator sterics and solvation effects, in a metal‐free condition.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/168301/1/anie202016393.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/168301/2/anie202016393_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/168301/3/anie202016393-sup-0001-misc_information.pd

    An Ion‐Pairing Approach to Stereoselective Metal‐Free Ring‐Opening Metathesis Polymerization

    Full text link
    Stereochemistry can have a profound impact on polymer and materials properties. Unfortunately, straightforward methods for realizing high levels of stereocontrolled polymerizations are often challenging to achieve. In a departure from traditional metal‐mediated ring‐opening metathesis polymerization (ROMP), we discovered a remarkably simple method for controlling alkene stereochemistry in photoredox mediated metal‐free ROMP. Ion‐pairing, initiator sterics, and solvation effects each had profound impact on the stereochemistry of polynorbornene (PNB). Simple modifications to the reaction conditions produced PNB with trans alkene content of 25 to >98 %. High cis content was obtained from relatively larger counterions, toluene as solvent, low temperatures (−78 °C), and initiators with low Charton values. Conversely, smaller counterions, dichloromethane as solvent, and enol ethers with higher Charton values enabled production of PNB with high trans content. Data from a combined experimental and computational investigation are consistent with the stereocontrolling step of the radical cationic mechanism proceeding under thermodynamic control.Stereoselective ring‐opening metathesis polymerization is achieved by non‐covalent interactions, such as ion‐pairing, initiator sterics and solvation effects, in a metal‐free condition.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/168268/1/ange202016393.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/168268/2/ange202016393_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/168268/3/ange202016393-sup-0001-misc_information.pd
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