At the forefront of ecosystems adversely affected by climate change, coral reefs are sensitive to anomalously high temperatures which disassociate (bleaching) photosynthetic symbionts (Symbiodinium) ...from coral hosts and cause increasingly frequent and severe mass mortality events. Susceptibility to bleaching and mortality is variable among corals, and is determined by unknown proportions of environmental history and the synergy of Symbiodinium- and coral-specific properties. Symbiodinium live within host tissues overlaying the coral skeleton, which increases light availability through multiple light-scattering, forming one of the most efficient biological collectors of solar radiation. Light-transport in the upper ~200 μm layer of corals skeletons (measured as 'microscopic' reduced-scattering coefficient, μ'(S,m)), has been identified as a determinant of excess light increase during bleaching and is therefore a potential determinant of the differential rate and severity of bleaching response among coral species.
Here we experimentally demonstrate (in ten coral species) that, under thermal stress alone or combined thermal and light stress, low-μ'(S,m) corals bleach at higher rate and severity than high-μ'(S,m) corals and the Symbiodinium associated with low-μ'(S,m) corals experience twice the decrease in photochemical efficiency. We further modelled the light absorbed by Symbiodinium due to skeletal-scattering and show that the estimated skeleton-dependent light absorbed by Symbiodinium (per unit of photosynthetic pigment) and the temporal rate of increase in absorbed light during bleaching are several fold higher in low-μ'(S,m) corals.
While symbionts associated with low-Formula: see text corals receive less total light from the skeleton, they experience a higher rate of light increase once bleaching is initiated and absorbing bodies are lost; further precipitating the bleaching response. Because microscopic skeletal light-scattering is a robust predictor of light-dependent bleaching among the corals assessed here, this work establishes μ'(S,m) as one of the key determinants of differential bleaching response.
In conjugated polymers, radiative recombination of excitons (electron-hole pairs) competes with nonradiative thermal relaxation pathways. We visualized exciton quenching induced by hole polarons in ...single-polymer chains in a device geometry. The distance-scale for quenching was measured by means of a new subdiffraction, single-molecule technique--bias-modulated intensity centroid spectroscopy--which allowed the extraction of a mean centroid shift of 14 nanometers for highly ordered, single-polymer nanodomains. This shift requires energy transfer over distances an order of magnitude greater than previously reported for bulk conjugated polymers and far greater than predicted by the standard mechanism for exciton quenching, the unbiased diffusion of free excitons to quenching sites. Instead, multistep "energy funneling" to trapped, localized polarons is the probable mechanism for polaron-induced exciton quenching.
In contrast to the detailed understanding of inorganic materials, researchers lack a comprehensive view of how the properties of bulk organic materials arise from their individual components. For ...conjugated polymers to eventually serve as low cost semiconductor layers in electronic devices, researchers need to better understand their functionality. For organics, traditional materials science measurements tend to destroy the species of interest, especially at low concentrations. However, fluorescence continues to be a remarkably flexible, relatively noninvasive tool for probing the properties of individual molecules and allows researchers to carry out a broad range of experiments based on a relatively simple concept. In addition, the sensitivity of single-molecule spectroscopy allows researchers to see the properties of an individual component that would be masked in the bulk phase. In this Account, we examine several photophysical properties of different conjugated polymers using single-molecule spectroscopy. In these experiments, we probed the relationship between the conformation of single conjugated polymer chains and the distance scale and efficiency of energy transfer within the polymer. Recent studies used polarization anisotropy measurements on single polymer chains to study chain folding following spin-casting from solution. This Account summarizes the effects of monomer regioregularity and backbone rigidity, by comparing a regiorandom phenylene vinylene (MEH-PPV) with both a regiorandom and regioregular thiophene (P3HT). Synthesis of novel polymers allowed us to explore the role of different conformation-directing inclusions in a PPV backbone. We showed that these inclusions control the conformation of individual chains and that molecular dynamics can predict these structural effects. In situ solvent vapor annealing studies explored the dynamics of polymer chains as well as the effect of solvent evaporation on the structural equilibrium of the polymer. We observed that a slower rate of solvent evaporation results in a narrow population of highly ordered polymer chains. These highly ordered single chains serve as a model system to probe the effect of conformation on energy transfer following excitation in single MEH-PPV polymer chains in two distinct experiments. In the first, we correlated the anisotropy of the fluorescence emission of individual chains with the anisotropy of their fluorescence excitation. Using this data, we derived a model for energy transfer in a conjugated polymer, simulating chromophores along a chain, coupled via Förster energy transfer. In the second experiment, super-resolution measurements demonstrated the ability of single-molecule spectroscopy to directly visualize energy transfer along a polymer chain embedded in a model device environment. A capacitive device allowed for controlled localization of hole polarons onto the polymer chain. These positive charges subsequently quenched local excitations, providing insight into the range of energy transfer in these single polymer molecules. As researchers continue to characterize conjugated polymer films and develop methods for creating multichain systems, single-molecule techniques will provide a greater understanding of how polymer morphology influences interchain interactions and will lead to a richer description of the electronic properties of bulk conjugated polymer films.
•The novel qPCR allowed the detection of zoonotic hookworms in dogs from Nigeria•Ancylostoma braziliense is detected for the first time in dogs in Nigeria•Ancylostoma braziliense is endemic in ...Nigeria and poses a zoonotic threat
A number of gastrointestinal parasites have been reported to infect dogs in Nigeria, some of which have zoonotic potential. Of these, hookworms are the most prevalent, with both Ancylostoma caninum and Uncinaria stenocephala reported in the country. In this study, we subjected 203 hookworm microscopy-positive samples of the 885 individual faecal samples collected from dogs in Nigeria to a recently developed multiplex qPCR for the detection and characterisation of canine hookworm species. The qPCR demonstrated a diagnostic sensitivity of 98% (95% CI 95-99.4) allowing the detection of A. caninum and A. braziliense in 81.3% (165/203, 95% CI 75.3-86.1) and 51.2% (104/203, 95% CI 44.4-58) of the microscopy-positive faecal samples of dogs from Nigeria, respectively and 34.5% (70/203, 95% CI 28.3-41.3) of mixed infections with both hookworm species.
The finding of A. braziliense is particularly worrisome given this is a well-known agent of persistent cutaneous larva migrans, commonly referred to as “creeping eruptions” in humans. Although this parasite has been diagnosed in locals and in people travelling in Nigeria suffering from dermatological illnesses, this represents the first molecular identification of A. braziliense in its canine reservoir in the country. These results update the occurrence and distribution of hookworm species affecting dogs in Nigeria highlighting the suitability of the newly developed multiplex qPCR assay as a high-throughput tool for the surveillance of zoonotic hookworms, globally.
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•First nationwide survey using morphological and molecular approaches reveals widespread infections of dogs in Nigeria with potentially zoonotic parasites.•Risk of infection is associated with free ...roaming dogs and those that do not receive regular deworming treatment.•The environment is prone to contamination with potentially zoonotic parasites from feces of stray dogs.•Mass deworming of dogs along with mass administration of anthelmintic to children should be considered in line with the One Health paradigm.
Dog feces may contain zoonotic parasites that contaminate the environment and serve as a potential source of infection to animals and humans. In this study, microscopic and molecular analyses were used to estimate the prevalence and intensity of gastrointestinal (GI) parasites and assess the risk factors for infection in 948 dogs in three climatically distinct zones of Nigeria. Zoonotic helminths including Strongyloides stercoralis, Ancylostoma braziliense, A. caninum and Toxocara canis were detected either as single or multiple infections in 377 (39.8 %) of dogs examined. At multiple logistic regression analyses, association was found between GI parasite infection and deworming practices and dog management. Regarding A. braziliense, A. caninum and T. canis infections, intensity of egg shedding was statistically associated with the age of the dogs and not with their sex or breed. The majority of GI parasite-positive dogs did not receive regular deworming treatment (59 %) and roamed freely (56 %) thereby constituting public health risk. This is the first nationwide survey and analyses of risk factors of GI parasites of dogs using molecular methods as confirmation of their identity. The zoonotic potential of these parasites is exacerbated by the lack of both operational national policies to control the population of free-roaming dogs and to promote responsible dog ownership, and veterinary public health programs for dogs.
The regioregularity of a conjugated polymer can greatly affect bulk film morphologies and properties. However, it remains unclear how regioregularity affects the conformation of isolated individual ...chains where interchain interactions are absent. Here, the effect of the regioregularity on the conformations adopted by regioregular (rr-) and regiorandom (rra-) poly(3-hexylthiophene) (P3HT) chains was studied using single molecule fluorescence excitation polarization spectroscopy. While every rr-P3HT chain within an ensemble was found to fold into a highly ordered conformation, single rra-P3HT chains adopted a wide variety of conformations, ranging from highly ordered to isotropic. This distribution is likely due to variations in the positions of nonhead-to-tail linkages of the side-chains along the backbone of the different polymer chains. Molecular dynamics simulation on atomistic models of rr- and rra-P3HT chains supports the effect of regioregularity on the collapsed conformations. These results demonstrate that side-chains govern the morphology of P3HT, even at the single chain level.
This paper describes the simultaneous measurement of excitation and emission anisotropy to visualize energy transfer in single chains of the prototypical conjugated polymer MEH-PPV, for samples with ...>70% of the single chains organized into extended, rod-like conformations. The uniformity and high degree of order of the single molecules in these experiments has allowed direct comparison of our experimental data to energy-transfer simulations in model polymer chains. Increases in average anisotropy from 0.62 to 0.74 from excitation to emission and average changes of <15° to the in-plane dipole principal orientation axis confirmed that energy was transferred to a relatively small number of sites in these highly ordered chains. This organization persisted even at large molecular weights (M n = 850 kDa). Electronic energy transfer in highly anisotropic model chains was simulated using an incoherent Förster-type mechanism to generate modulation depth histograms in good agreement with the observed data, as well as ensemble emission energies consistent with previously reported results. In these ordered model chains, excitons migrated an average of 6 nm before emission. This distance, far larger than the radius for single-step FRET, implies that energy transfer in MEH-PPV is a multistep funneling process.
Claims data can be leveraged to study rare diseases such as Guillain-Barré Syndrome (GBS), a neurological autoimmune condition. It is difficult to accurately measure and distinguish true cases of ...disease with claims without a validated algorithm. Our objective was to identify the best-performing algorithm for identifying incident GBS cases in Medicare fee-for-service claims data using chart reviews as the gold standard.
This was a multi-center, single institution cohort study from 2015 to 2019 that used Medicare-linked electronic health record (EHR) data. We identified 211 patients with a GBS diagnosis code in any position of an inpatient or outpatient claim in Medicare that also had a record of GBS in their electronic medical record. We reported the positive predictive value (PPV = number of true GBS cases/total number of GBS cases identified by the algorithm) for each algorithm tested. We also tested algorithms using several prevalence assumptions for false negative GBS cases and calculated a ranked sum for each algorithm's performance.
We found that 40 patients out of 211 had a true case of GBS. Algorithm 17, a GBS diagnosis in the primary position of an inpatient claim and a diagnostic procedure within 45 days of the inpatient admission date, had the highest PPV (PPV = 81.6%, 95% CI (69.3, 93.9). Across three prevalence assumptions, Algorithm 15, a GBS diagnosis in the primary position of an inpatient claim, was favored (PPV = 79.5%, 95% CI (67.6, 91.5).
Our findings demonstrate that patients with incident GBS can be accurately identified in Medicare claims with a chart-validated algorithm. Using large-scale administrative data to study GBS offers significant advantages over case reports and patient repositories with self-reported data, and may be a potential strategy for the study of other rare diseases.
•Guillain-Barré Syndrome (GBS) is rare and claims data offer larger sample sizes.•Tested algorithms for identifying GBS in claims with chart review gold standard.•Primary inpatient diagnosis + procedure had the highest positive predictive value.•Primary inpatient diagnosis was favored across three GBS prevalence assumptions.•We validated several algorithms for identifying GBS cases in Medicare claims.
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