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Contra-thermodynamic Olefin Isomerization by Chain-Walking Hydrofunctionalization and Formal Retro-hydrofunctionalization.

We report a contra-thermodynamic isomerization of internal olefins to terminal olefins driven by redox reactions and formation of Si-F bonds. This process involves chain-walking hydrosilylation of internal olefins and subsequent formal retro-hydrosilylation. The process rests upon the high activities of platinum hydrosilylation catalysts for isomerization of metal alkyl intermediates and a new, metal-free process for the conversion of alkylsilanes to alkenes. By this approach, 1,2-disubstituted and trisubstituted olefins are converted to terminal olefins

Adverse Childhood Experiences and Risk of Binge Drinking and Drunkenness in Middle-Aged Finnish Men

Objective. The purpose of this study was to investigate associations between adverse childhood experiences and binge drinking and drunkenness in adulthood using both historical and recalled data from childhood. Methods. Data on childhood adverse experiences were collected from school health records and questionnaires completed in adulthood. Adulthood data were obtained from the baseline examinations of the male participants (n = 2682) in the Kuopio Ischaemic Heart Disease Risk Factor Study (KIHD) in 1984–1989 from eastern Finland. School health records from the 1930s to 1950s were available for a subsample of KIHD men (n = 952). Results. According to the school health records, men who had adverse childhood experiences had a 1.51-fold (95% CI 1.05 to 2.18) age- and examination-year adjusted odds of binge drinking in adulthood. After adjustment for socioeconomic position in adulthood or behavioural factors in adulthood, the association remained unchanged. Adjustment for socioeconomic position in childhood attenuated these effects. Also the recalled data showed associations with adverse childhood experiences and binge drinking with different beverages. Conclusions. Our findings suggest that childhood adversities are associated with increased risk of binge drinking in adulthood

Role of DNA sequences outside the cores of DNase hypersensitive sites (HSs) in functions of the β-globin locus control region. Domain opening and synergism between HS2 and HS3

The roles of each DNase hypersensitive site (HS), and the DNA sequences between them, in the activity of the locus control region of the mammalian β-globin gene domain were examined by placing human and rabbit restriction fragments containing the cores of HS2, HS3, HS4, and HS5, along with varying amounts of flanking DNA, upstream of a hybrid ε-globin-luciferase reporter gene and testing for effects on expression both prior to and after integration into the chromosomes of K562 cells, a human erythroid cell line. Prior to integration, fragments containing HS2 enhanced expression to the greatest extent, and the modest enhancement by some fragments containing HS3 correlated with the presence of a well-conserved binding site for AP1/NFE2. The stronger effects of larger locus control region DNA fragments in clones of stably transfected cells indicates a role for sequences outside the HS cores after integration into the genome. The strong effect of a 1.9-kilobase HindIII fragment containing HS3 after, but not prior to, integration argues for the presence of a chromatin domain-opening activity. Use of a rabbit DNA fragment containing both HS2 and HS3 demonstrated a synergistic interaction between the two HSs when their natural context and spacing are preserved

Conservation genetics of cyprinid fishes in the upper Nueces River basin in central Texas

Sequences of the mitochondrial (mt) NADH dehydrogenase subunit 5 gene (ND5) were acquired to assess genetic diversity and female effective population size (Nef) of two forms of Cyprinella (C. lepida and C. sp. cf lepida) and two species of Dionda (D. serena and D. texensis) in headwaters of three rivers in the upper Nueces River basin in central Texas. As documented in prior studies, two divergent clades of haplotypes of mtDNA were found in both genera: one in the Frio and Sabinal rivers, representing C. lepida and D. serena; one in the Nueces River, representing C. sp. cf lepida and D. texensis. Levels of variation in mtDNA from C. lepida in the Sabinal River and D. serena in the Frio and Sabinal rivers were comparable to or considerably lower than values documented for populations of several threatened or endangered cyprinids. Estimates of Nef for C. lepida in the Frio River and C. sp. cf lepida in the Nueces River were low, suggesting that adaptive genetic variation through time may be compromised. Of all populations sampled, only D. texensis in the Nueces River appears at present to be genetically stable demographically. An unexpected finding was two individuals resembling C. lepida in the Frio River with a haplotype referable to C. sp. cf lepida; the origin of these individuals is unknown. Two other individuals resembling C. lepida but with haplotypes of mtDNA referable to C. venusta were found in the Frio River and presumably represent relatively recent hybrids. Results of our study indicate that C. lepida, C. sp. cf lepida, and D. serena in the upper Nueces River basin, especially in the Sabinal River drainage, are at appreciable genetic risk

Legacy effects of long-term nitrogen fertilizer application on the fate of nitrogen fertilizer inputs in continuous maize

Nitrogen fertilizer management can impact soil organic C (SOC) stocks in cereal-based cropping systems by regulating crop residue inputs and decomposition rates. However, the impact of long-term N fertilizer management, and associated changes in SOC quantity and quality, on the fate of N fertilizer inputs is uncertain. Using two 15-year N fertilizer rate experiments on continuous maize (Zea mays L.) in Iowa, which have generated gradients of SOC, we evaluated the legacy effects of N fertilizer inputs on the fate of added N. Across the historical N fertilizer rates, which ranged from 0 to 269 kg N ha−1 yr−1, we applied isotopically-labeled N fertilizer at the empirically-determined site-specific agronomic optimum rate (202 kg N ha−1 at the central location and 269 kg N ha−1 at the southern location) and measured fertilizer recovery in crop and soil pools, and, by difference, environmental losses. Crop fertilizer N recovery efficiency (NREcrop) at physiological maturity averaged 44% and 14% of applied N in central Iowa and southern Iowa, respectively (88 kg N ha−1 and 37 kg N ha−1, respectively). Despite these large differences in NREcrop, the response to historical N rate was remarkably similar across both locations: NREcrop was greatest at low and high historical N rates, and least at the intermediate rates. Decreasing NREcrop from low to intermediate historical N rates corresponded to a decline in early-season fertilizer N recovery in the relatively slow turnover topsoil mineral-associated organic matter pool (0–15 cm), while increasing NREcrop from intermediate to high historical N rates corresponded to an increase in early-season fertilizer N recovery in the relatively fast turnover topsoil particulate organic matter pool and an increase in crop yield potential. Despite the variation in NREcropalong the historical N rate gradient, we did not detect an effect of historical N rate on environmental losses during the growing season, which averaged 34% and 69% of fertilizer N inputs at the central and southern locations, respectively (69 kg N ha−1 and 185 kg N ha−1, respectively). Our results suggest that, while beneficial for SOC storage over the long term, fertilizing at the agronomic optimum N rate can lead to significant environmental N losses

Simultaneous MQMAS NMR experiments for two half-integer quadrupolar nuclei

A procedure to acquire two Multiple-Quantum Magic Angle Spinning (MQMAS) NMR experiments with the same instrument time is presented. A triply tuned probe is utilized with multiple receivers to collect data with staggered acquisitions and thus more efficiently use the instrument time. The data for one nucleus is collected during the recovery delay of the other nucleus, and vice versa. The instrument time is reduced to 60-80% of the time needed for the single acquisition collection Specifically our approach is presented for recording triple-quantum (3Q) 17O and either 3Q or quintuple-quantum (5Q) 27Al MAS NMR spectra of a 1.18Na2O•5SiO2•Al2O3 glass gel

N-Terminal Pro–B-Type Natriuretic Peptide in the Emergency Department: The ICON-RELOADED Study

Background Contemporary reconsideration of diagnostic N-terminal pro–B-type natriuretic peptide (NT-proBNP) cutoffs for diagnosis of heart failure (HF) is needed. Objectives This study sought to evaluate the diagnostic performance of NT-proBNP for acute HF in patients with dyspnea in the emergency department (ED) setting. Methods Dyspneic patients presenting to 19 EDs in North America were enrolled and had blood drawn for subsequent NT-proBNP measurement. Primary endpoints were positive predictive values of age-stratified cutoffs (450, 900, and 1,800 pg/ml) for diagnosis of acute HF and negative predictive value of the rule-out cutoff to exclude acute HF. Secondary endpoints included sensitivity, specificity, and positive (+) and negative (−) likelihood ratios (LRs) for acute HF. Results Of 1,461 subjects, 277 (19%) were adjudicated as having acute HF. The area under the receiver-operating characteristic curve for diagnosis of acute HF was 0.91 (95% confidence interval [CI]: 0.90 to 0.93; p < 0.001). Sensitivity for age stratified cutoffs of 450, 900, and 1,800 pg/ml was 85.7%, 79.3%, and 75.9%, respectively; specificity was 93.9%, 84.0%, and 75.0%, respectively. Positive predictive values were 53.6%, 58.4%, and 62.0%, respectively. Overall LR+ across age-dependent cutoffs was 5.99 (95% CI: 5.05 to 6.93); individual LR+ for age-dependent cutoffs was 14.08, 4.95, and 3.03, respectively. The sensitivity and negative predictive value for the rule-out cutoff of 300 pg/ml were 93.9% and 98.0%, respectively; LR− was 0.09 (95% CI: 0.05 to 0.13). Conclusions In acutely dyspneic patients seen in the ED setting, age-stratified NT-proBNP cutpoints may aid in the diagnosis of acute HF. An NT-proBNP <300 pg/ml strongly excludes the presence of acute HF

Molecular epidemiology of NDM-1-producing Enterobacteriaceae and Acinetobacter baumannii isolates from Pakistan

The molecular epidemiology of 66 NDM-producing isolates from 2 Pakistani hospitals was investigated, with their genetic relatedness determined using repetitive sequence-based PCR (Rep-PCR). PCR-based replicon typing and screening for antibiotic resistance genes encoding carbapenemases, other β-lactamases, and 16S methylases were also performed. Rep-PCR suggested a clonal spread of Enterobacter cloacae and Escherichia coli. A number of plasmid replicon types were identified, with the incompatibility A/C group (IncA/C) being the most common (78%). 16S methylase-encoding genes were coharbored in 81% of NDM-producing Enterobacteriaceae. Copyrigh