Sulfur and Selenium Ylide Bond Enthalpies

The bond dissociation enthalpies (BDEs) of sulfur and selenium ylides have been estimated by applying MP2/6-311++G(3df,2p)//MP2/6-31G(d,p), G3, and other computational methods. Computed sulfoxide bond enthalpies were compared to experimental results to ensure the reliability of the computational methods before extending to related compounds. The examined ylides include the following:  sulfoxides, sulfilimines, S,C-sulfonium ylides, and selenoxides. Selenoxides have BDEs about 10 kcal/mol smaller than the corresponding sulfoxides. N-H sulfilimines and CH2-S,C-sulfonium ylides have low BDEs, unless the sulfilimine or S,C-sulfonium ylide is stabilized by an electronegative substituent on N or C, respectively. Incorporation of the S or Se into a thiophene or selenophene-type ring lowers the BDE for the ylide

Harvest Demographics of Temperate-breeding Canada Geese in South Dakota, 1967–1995

In South Dakota, breeding giant Canada geese (Branta canadensis maxima) have increased substantially, and harvest management strategies have been implemented to maximize hunting opportunity (e.g., special early-September seasons) on local, as well as molt-migrant giant Canada geese (B. c. interior) while still protecting lesser abundant Arcticbreeding Canada geese and cackling geese (e.g., B. hutchinsii, B. minima). Information on important parameters, such as survival and recovery rates, are generally lacking for giant Canada geese in the northern Great Plains. Patterns in Canada goose band recoveries can provide insight into the distribution, chronology, and harvest pressures to which a given goose population segment is exposed. We studied spatial and temporal recovery patterns of molting Canada geese during annual banding efforts in South Dakota between 1967 and 1995. Recovery rates (% ± SE) for Canada geese increased over time in both western South Dakota (0.034 ± 0.005 [1967 to 1976], 0.056 ± 0.009 [1977 to 1986]) and eastern (0.026 ± 0.002 [1967 to 1978], 0.058 ± 0.003 [1987 to 1995]) South Dakota. Although recovery rates for Canada geese west of the Missouri River (WR) and east of the Missouri River (ER) were relatively similar, recovery distribution and harvest chronology indicate spatial and temporal differences for geese banded in these 2 geographic regions. Overall, Canada geese banded in South Dakota were recovered in 23 states and 5 Canadian provinces, and recovery distribution varied relative to banding region. Distribution of recoveries suggests a south-southwesterly movement for WR-banded geese compared to a south-southeasterly movement for ERbanded geese. For WR-banded geese, 40 to 52% and 30 to 34% of direct and indirect recoveries, respectively, occurred in December. In contrast, for ER-banded geese, 19 to 38% and 15 to 19% of direct and indirect recoveries, respectively, occurred in December. Waterfowl managers need to consider that recovery rates and harvest chronology of banded giant Canada geese may vary geographically within a state or province. Refinement of harvest management strategies at multiple spatial scales may be required

Evaluation of SARS-CoV-2 antibody point of care devices in the laboratory and clinical setting

SARS-CoV-2 antibody tests have been marketed to diagnose previous SARS-CoV-2 infection and as a test of immune status. There is a lack of evidence on the performance and clinical utility of these tests. We aimed to carry out an evaluation of 14 point of care (POC) SARS-CoV-2 antibody tests. Serum from participants with previous RT-PCR (real-time polymerase chain reaction) confirmed SARS-CoV-2 infection and pre-pandemic serum controls were used to determine specificity and sensitivity of each POC device. Changes in sensitivity with increasing time from infection were determined on a cohort of study participants. Corresponding neutralising antibody status was measured to establish whether the detection of antibodies by the POC device correlated with immune status. Paired capillary and serum samples were collected to ascertain whether POC devices performed comparably on capillary samples. Sensitivity and specificity varied between the POC devices and in general did not meet the manufacturers’ reported performance characteristics, which signifies the importance of independent evaluation of these tests. The sensitivity peaked at ≥20 days following onset of symptoms, however sensitivity of 3 of the POC devices evaluated at extended time points showed that sensitivity declined with time. This was particularly marked at >140 days post infection. This is relevant if the tests are to be used for sero-prevalence studies. Neutralising antibody data showed that positive antibody results on POC devices did not necessarily confer high neutralising antibody titres, and that these POC devices cannot be used to determine immune status to the SARS-CoV-2 virus. Comparison of paired serum and capillary results showed that there was a decline in sensitivity using capillary blood. This has implications in the utility of the tests as they are designed to be used on capillary blood by the general population

3D Buried Utility Location Using A Marching-Cross-Section Algorithm for Multi-sensor Data Fusion

We address the problem of accurately locating buried utility segments by fusing data from multiple sensors using a novel marching-cross-section (MCS) algorithm. Five types of sensors are used in this work: Ground Penetrating Radar (GPR), Passive Magnetic Fields (PMF), Magnetic Gradiometer (MG), Low Frequency Electromagnetic Fields (LFEM), and Vibro-acoustics (VA). As part of the MCS algorithm, a novel formulation of the extended Kalman filter (EKF) is proposed for marching existing utility tracks from a scan cross section (scs) to the next one; novel rules for initializing utilities based on hypothesized detections on the first scs and for associating predicted utility tracks with hypothesized detections in the following scss are introduced. Algorithms are proposed for generating virtual scan lines based on given hypothesized detections when different sensors do not share common scan lines, or when only the coordinates of the hypothesized detections are provided without any information of the actual survey scan lines. The performance of the proposed system is evaluated with both synthetic data and real data. The experimental results in this work demonstrate that the proposed MCS algorithm can locate multiple buried utility segments simultaneously, including both straight and curved utilities and can separate intersecting segments. By using the probabilities of a hypothesized detection being a pipe or a cable together with its 3D coordinates, the MCS algorithm is able to discriminate a pipe and a cable close to each other. The MCS algorithm can be used for both post and on-site processing. When it is used on site, the detected tracks on the current scs can help to determine the location and direction of the next scan line. The proposed “multi-utility multi-sensor” system has no limit to the number of buried utilities or the number of sensors, and the more sensor data used the more buried utility segments can be detected with more accurate location and orientation

SCYX-7158, an Orally-Active Benzoxaborole for the Treatment of Stage 2 Human African Trypanosomiasis

Human African trypanosomiasis (HAT) is caused by infection with the parasite Trypanosoma brucei and is an important public health problem in sub-Saharan Africa. New, safe, and effective drugs are urgently needed to treat HAT, particularly stage 2 disease where the parasite infects the brain. Existing therapies for HAT have poor safety profiles, difficult treatment regimens, limited effectiveness, and a high cost of goods. Through an integrated drug discovery project, we have discovered and optimized a novel class of boron-containing small molecules, benzoxaboroles, to deliver SCYX-7158, an orally active preclinical drug candidate. SCYX-7158 cured mice infected with T. brucei, both in the blood and in the brain. Extensive pharmacokinetic characterization of SCYX-7158 in rodents and non-human primates supports the potential of this drug candidate for progression to IND-enabling studies in advance of clinical trials for stage 2 HAT

Habitat Assessment of Non-Wadeable Rivers in Michigan

Habitat evaluation of wadeable streams based on accepted protocols provides a rapid and widely used adjunct to biological assessment. However, little effort has been devoted to habitat evaluation in non-wadeable rivers, where it is likely that protocols will differ and field logistics will be more challenging. We developed and tested a non-wadeable habitat index (NWHI) for rivers of Michigan, where non-wadeable rivers were defined as those of order ≥5, drainage area ≥1600 km 2 , mainstem lengths ≥100 km, and mean annual discharge ≥15 m 3 /s. This identified 22 candidate rivers that ranged in length from 103 to 825 km and in drainage area from 1620 to 16,860 km 2 . We measured 171 individual habitat variables over 2-km reaches at 35 locations on 14 rivers during 2000–2002, where mean wetted width was found to range from 32 to 185 m and mean thalweg depth from 0.8 to 8.3 m. We used correlation and principal components analysis to reduce the number of variables, and examined the spatial pattern of retained variables to exclude any that appeared to reflect spatial location rather than reach condition, resulting in 12 variables to be considered in the habitat index. The proposed NWHI included seven variables: riparian width, large woody debris, aquatic vegetation, bottom deposition, bank stability, thalweg substrate, and off-channel habitat. These variables were included because of their statistical association with independently derived measures of human disturbance in the riparian zone and the catchment, and because they are considered important in other habitat protocols or to the ecology of large rivers. Five variables were excluded because they were primarily related to river size rather than anthropogenic disturbance. This index correlated strongly with indices of disturbance based on the riparian (adjusted R 2 = 0.62) and the catchment (adjusted R 2 = 0.50), and distinguished the 35 river reaches into the categories of poor (2), fair (19), good (13), and excellent (1). Habitat variables retained in the NWHI differ from several used in wadeable streams, and place greater emphasis on known characteristic features of larger rivers.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/41269/1/267_2004_Article_141.pd

The STAT5b Pathway Defect and Autoimmunity

The signal transducer and activator of transcription (STAT) 5b is a universal transcription factor that plays key biological roles in allergic diseases, immunodeficiencies, autoimmunities, cancers, hematological diseases, growth disorders, and lung diseases. The identification of distinct pathological manifestations of STAT5b deficiency in humans has highlighted the critical role of the STAT5b pathway. Proper gene transcription at IL-2R α, FOXP3, Bcl-2, and growth hormone (GH) associated loci are thought to be associated with normal STAT5b transcriptional activity. These genes are thought to play important roles in allergy/autoimmunity, immunodeficiency, cancer/anemia, and growth, respectively. The STAT5A and STAT5B genes are collocated on 17q11. Although these two monomeric proteins exhibit peptide sequence similarities of >90%, it is known through observations of STAT5b deficient subjects that STAT5a and STAT5b are not fully redundant in humans. Patients with STAT5b deficiency have decreased numbers of regulatory CD4(+)CD25(high) T cell (Treg) despite their STAT5a levels being normal. Prior studies on STAT5b deficient subjects have revealed immunological aberrations associated with the following disease phenotype: modest lymphopenia and decreased populations of Treg, γ−δ T cells, and natural killer (NK) cells. Most subjects with STAT5b deficiency show severe eczema, and autoimmune disease (juvenile idiopathic arthritis, autoimmune thyroiditis, idiopathic thrombocytic purpura) which are thought to be associated with Treg dysfunction. We will review the likely pathophysiological mechanisms associated with STAT5b deficiency

Sulfur and Selenium Ylide Bond Enthalpies

The bond dissociation enthalpies (BDEs) of sulfur and selenium ylides have been estimated by applying MP2/6-311++G(3df,2p)//MP2/6-31G(d,p), G3, and other computational methods. Computed sulfoxide bond enthalpies were compared to experimental results to ensure the reliability of the computational methods before extending to related compounds. The examined ylides include the following:  sulfoxides, sulfilimines, S,C-sulfonium ylides, and selenoxides. Selenoxides have BDEs about 10 kcal/mol smaller than the corresponding sulfoxides. N-H sulfilimines and CH2-S,C-sulfonium ylides have low BDEs, unless the sulfilimine or S,C-sulfonium ylide is stabilized by an electronegative substituent on N or C, respectively. Incorporation of the S or Se into a thiophene or selenophene-type ring lowers the BDE for the ylide.Reprinted (adapted) with permission from The Journal of Organic Chemistry, 72(22); 8235-8242. Doi: 10.1021/jo0711438. Copyright 2007 American Chemical Society.</p