1,751 research outputs found

    Forging Fluorine-Containing Quaternary Stereocenters by a Light-Driven Organocatalytic Aldol Desymmetrization Process

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    Reported herein is a light-triggered organocatalytic strategy for the desymmetrization of achiral 2-fluoro-substi- tuted cyclopentane-1,3-diketones. The chemistry is based on an intermolecular aldol reaction of photochemically generated hydroxy-o-quinodimethanes and simultaneously forges two adjacent fully substituted carbon stereocenters, with one bearing a stereogenic carbon–fluorine unit. The method uses readily available substrates, a simple chiral organocatalyst, and mild reaction conditions to afford an array of highly function- alized chiral 2-fluoro-3-hydroxycyclopentanones

    Chemical warfare simulant-responsive polymer nanocomposites: Synthesis and evaluation

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    Nanomaterials that undergo a physical change upon chemical warfare agent (CWA) exposure can potentially be used in detectors to warn soldiers of their presence or in fabrics to provide on‐demand protection. In this study, hybrid nanoparticles (NPs) were prepared by grafting a CWA‐responsive polymer from a silicon dioxide (SiO₂) surface using ring opening metathesis polymerization; the covalent functionalization of the polymers on the NP surface was confirmed by gel permeation chromatography, dynamic light scattering, and transmission electron microscopy analysis. The polymer‐grafted SiO₂ NPs were found to undergo a pronounced decrease (approximately 200 nm) in their hydrodynamic radius upon exposure to CWA simulants trifluoroacetic acid and diethyl chlorophosphate in toluene. This decrease in hydrodynamic radius is attributed to the electrophile‐mediated ionization of the triarylmethanol responsive unit and represents a rare example of polycation formation leading to polymer chain collapse. We have ascribed this ionization‐induced collapse to the formation of a favorable stacking interaction between the planar triarylcations. These studies have important implications for the development of breathable fabrics that can provide on‐demand protection for soldiers in combat situations. Keywords: nanocomposites; stimuli-responsive; ROMP; organophosphates; triarylmethanolsDefense Threat Reduction Agency (DTRA) (Contract BA12PHM123

    Pre-pregnancy predictors of hypertension in pregnancy among Aboriginal and Torres Strait Islander women in north Queensland, Australia; a prospective cohort study

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    BACKGROUND Compared to other Australian women, Indigenous women are frequently at greater risk for hypertensive disorders of pregnancy. We examined pre-pregnancy factors that may predict hypertension in pregnancy in a cohort of Aboriginal and Torres Strait Islander women in north Queensland. METHODS Data on a cohort of 1009 Indigenous women of childbearing age (15–44 years) who participated in a 1998–2000 health screening program in north Queensland were combined with 1998–2008 Queensland hospitalisations data using probabilistic data linkage. Data on the women in the cohort who were hospitalised for birth (n = 220) were further combined with Queensland perinatal data which identified those diagnosed with hypertension in pregnancy. RESULTS Of 220 women who gave birth, 22 had hypertension in the pregnancy after their health check. The mean age of women with and without hypertension was similar (23.7 years and 23.9 years respectively) however Aboriginal women were more affected compared to Torres Strait Islanders. Pre-pregnancy adiposity and elevated blood pressure at the health screening program were predictors of a pregnancy affected by hypertension. After adjusting for age and ethnicity, each 1 cm increase in waist circumference showed a 4% increased risk for hypertension in pregnancy (PR 1.04; 95% CI; 1.02-1.06); each 1 point increase in BMI showed a 9% adjusted increase in risk (1.09; 1.04-1.14). For each 1 mmHg increase in baseline systolic blood pressure there was an age and ethnicity adjusted 6% increase in risk and each 1 mmHg increase in diastolic blood pressure showed a 7% increase in risk (1.06; 1.03-1.09 and 1.07; 1.03-1.11 respectively). Among those free of diabetes at baseline, the presence of the metabolic syndrome (International Diabetes Federation criteria) predicted over a three-fold increase in age-ethnicity-adjusted risk (3.5; 1.50-8.17). CONCLUSIONS Pre-pregnancy adiposity and features of the metabolic syndrome among these young Aboriginal and Torres Strait Islander women track strongly to increased risk of hypertension in pregnancy with associated risks to the health of babies.Sandra K Campbell, John Lynch, Adrian Esterman and Robyn McDermot

    Carbon(sp 3 )Fluorine Bond‐Forming Reductive Elimination from Palladium(IV) Complexes

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    Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/90585/1/anie_201107816_sm_miscellaneous_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/90585/2/3414_ftp.pd

    Carbon(sp 3 )Fluorine Bond‐Forming Reductive Elimination from Palladium(IV) Complexes

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    Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/90520/1/ange_201107816_sm_miscellaneous_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/90520/2/3470_ftp.pd

    Manufacturing and Testing of a Variable Chord Extension for Helicopter Rotor Blades

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    Helicopters are still an indispensable addition to aviation in this day and age. They are characterized by their ability to master both forward flight and hover. These characteristics result in a wide range of possible operations. Key for the design of the rotor blades is a blade design that always represents a compromise between the different flight conditions, which enables save and efficient flight in the various flight conditions. In order to operate the rotor blade even more efficient in all flight conditions, a new morphing concept, the so-called linear variable chord extension, has been developed. Here, the blade chord length in the root area is changed with the help of an elastic skin to adapt it to the respective flight condition. The simulations performed for this concept showed a promising increase in overall helicopter performance. The fabrication of the resulting demonstra- tor as well as the tests in the whirl-tower and wind tunnel will be presented in this paper. The results of the tests show that the concept of linear variable chord extension has a positive influence and a great potential for hovering flight
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