136 research outputs found

    Accuracy and consistency of grass pollen identification by human analysts using electron micrographs of surface ornamentation

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    • Premise of the study: Humans frequently identify pollen grains at a taxonomic rank above species. Grass pollen is a classic case of this situation, which has led to the development of computational methods for identifying grass pollen species. This paper aims to provide context for these computational methods by quantifying the accuracy and consistency of human identification. • Methods: We measured the ability of nine human analysts to identify 12 species of grass pollen using scanning electron microscopy images. These are the same images that were used in computational identifications. We have measured the coverage, accuracy, and consistency of each analyst, and investigated their ability to recognize duplicate images. • Results: Coverage ranged from 87.5% to 100%. Mean identification accuracy ranged from 46.67% to 87.5%. The identification consistency of each analyst ranged from 32.5% to 87.5%, and each of the nine analysts produced considerably different identification schemes. The proportion of duplicate image pairs that were missed ranged from 6.25% to 58.33%. • Discussion: The identification errors made by each analyst, which result in a decline in accuracy and consistency, are likely related to psychological factors such as the limited capacity of human memory, fatigue and boredom, recency effects, and positivity bias

    Constrained TRPV1 agonists synthesized via silver-mediated intramolecular azo-methine ylide cycloaddition of α-iminoamides

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    As part of an effort to identify agonists of TRPV1, a peripheral sensory nerve ion channel, high throughput screening of the NIH Small Molecule Repository (SMR) collection identified MLS002174161, a pentacyclic benzodiazepine. A synthesis effort was initiated that ultimately afforded racemic seco analogs 12 of the SMR compound via a silver mediated intramolecular [3+2] cycloaddition of an azo-methine ylide generated from α-iminoamides 11. The cycloaddition set four contiguous stereocenters and, in some cases, also spontaneously afforded imides 13 from 12. The synthesis of compounds 12, the features that facilitated the conversion of 12–13, and their partial agonist activity against TRPV1 are discussed

    Deactivation of Sn-Beta zeolites caused by structural transformation of hydrophobic to hydrophilic micropores during aqueous-phase glucose isomerization

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    The structural changes underlying the deactivation of Sn-Beta zeolites under aqueous-phase reaction conditions at elevated temperatures (373 K) are investigated using spectroscopic characterization and site titration techniques together with turnover rates for glucose isomerization, a well-understood probe reaction for which changes in measured rates can be ascribed to specific changes in catalyst structure. In the case of hydrophobic, low-defect Sn-Beta zeolites (Sn-Beta-F), treatment in hot liquid water (373 K) for short times (3 h) to hot liquid water causes turnover rates to decrease and approach values characteristic of hydrophilic, defect-rich Sn-Beta zeolites (Sn-Beta-OH). In contrast, turnover rates on hydrophilic Sn-Beta-OH zeolites are insensitive to the duration of hot liquid water exposure prior to reaction. Activation and deactivation phenomena on Sn-Beta-F zeolites occur concomitantly with the formation of silanol defects (by ∼2–10×) with increasing durations (0–24 h) of hot water treatment, despite negligible differences in open and closed Sn site speciation as quantified ex situ by CD_3CN IR spectra. Mechanistic interpretations of these phenomena suggest that silanol groups present at low densities serve as binding sites for water molecules and clusters, which confer enthalpic stability to kinetically-relevant hydride-shift transition states and increase turnover rates, while silanol groups present in higher densities stabilize extended hydrogen-bonded water networks, which entropically destabilize kinetically-relevant transition states and decrease turnover rates. Intraporous voids within hydrophobic Sn-Beta-F zeolites become increasingly hydrophilic as silanol groups are formed by hydrolysis of framework siloxane bridges with increasing durations of water treatment, thereby decreasing aqueous-phase glucose isomerization turnover rates (per open Sn site). These findings suggest design strategies that suppress framework hydrolysis would attenuate the deactivation of Lewis acid zeolites in aqueous media

    Deactivation of Sn-Beta zeolites caused by structural transformation of hydrophobic to hydrophilic micropores during aqueous-phase glucose isomerization

    Get PDF
    The structural changes underlying the deactivation of Sn-Beta zeolites under aqueous-phase reaction conditions at elevated temperatures (373 K) are investigated using spectroscopic characterization and site titration techniques together with turnover rates for glucose isomerization, a well-understood probe reaction for which changes in measured rates can be ascribed to specific changes in catalyst structure. In the case of hydrophobic, low-defect Sn-Beta zeolites (Sn-Beta-F), treatment in hot liquid water (373 K) for short times (3 h) to hot liquid water causes turnover rates to decrease and approach values characteristic of hydrophilic, defect-rich Sn-Beta zeolites (Sn-Beta-OH). In contrast, turnover rates on hydrophilic Sn-Beta-OH zeolites are insensitive to the duration of hot liquid water exposure prior to reaction. Activation and deactivation phenomena on Sn-Beta-F zeolites occur concomitantly with the formation of silanol defects (by ∼2–10×) with increasing durations (0–24 h) of hot water treatment, despite negligible differences in open and closed Sn site speciation as quantified ex situ by CD_3CN IR spectra. Mechanistic interpretations of these phenomena suggest that silanol groups present at low densities serve as binding sites for water molecules and clusters, which confer enthalpic stability to kinetically-relevant hydride-shift transition states and increase turnover rates, while silanol groups present in higher densities stabilize extended hydrogen-bonded water networks, which entropically destabilize kinetically-relevant transition states and decrease turnover rates. Intraporous voids within hydrophobic Sn-Beta-F zeolites become increasingly hydrophilic as silanol groups are formed by hydrolysis of framework siloxane bridges with increasing durations of water treatment, thereby decreasing aqueous-phase glucose isomerization turnover rates (per open Sn site). These findings suggest design strategies that suppress framework hydrolysis would attenuate the deactivation of Lewis acid zeolites in aqueous media

    Large-Scale Sidereal Anisotropy of Galactic Cosmic-Ray Intensity Observed by the Tibet Air Shower Array

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    We present the large-scale sidereal anisotropy ofgalactic cosmic-ray intensity in the multi-TeV region observed with the Tibet-IIIair shower array during the period from 1999 through 2003. The sidereal daily variation of cosmic rays observed in this experiment shows an excess of relative intensity around 474\sim7 hours local sidereal time, as well as a deficit around 12 hours local sidereal time. While the amplitude of the excess is not significant when averaged over all declinations, the excess in individual declinaton bands becomes larger and clearer as the viewing direction moves toward the south. The maximum phase of the excess intensity changes from \sim7 at the northern hemisphere to \sim4 hours at the equatorial region. We also show that both the amplitude and the phase of the first harmonic vector of the daily variation are remarkably independent of primary energy in the multi-TeV region. This is the first result determining the energy and declination dependences of the full 24-hour profiles of the sidereal daily variation in the multi-TeV region with a single air shower experiment.Comment: 13 pages, 3 figures, 1 table. Accepted for publication in ApJ

    Retrieving C and O Abundance of HR 8799 c by Combining High- and Low-Resolution Data

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    The formation and evolution pathway for the directly-imaged multi-planetary system HR 8799 remains mysterious. Accurate constraints on the chemical composition of the planetary atmosphere(s) are key to solving the mystery. We perform a detailed atmospheric retrieval on HR 8799~c to infer the chemical abundances and abundance ratios using a combination of photometric data along with low- and high-resolution spectroscopic data (R\sim20-35,000). We specifically retrieve [C/H], [O/H], and C/O and find them to be 0.550.39+0.36^{+0.36}_{-0.39}, 0.470.32+0.31^{+0.31}_{-0.32}, and 0.670.15+0.12^{+0.12}_{-0.15} at 68\% confidence. The super-stellar C and O abundances, yet a stellar C/O ratio, reveal a potential formation pathway for HR 8799~c. Planet c, and likely the other gas giant planets in the system, formed early on (likely within \sim1 Myr), followed by further atmospheric enrichment in C and O through the accretion of solids beyond the CO iceline. The enrichment either preceded or took place during the early phase of the inward migration to the planet current locations.Comment: 19 pages, 6 figures, 3 tables, accepted to AAS journal
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