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91.
An Integrated Experimental and Computational Approach for Characterizing the Kinetics and Mechanism of Triadimefon Racemization 下载免费PDF全文
Qianyi Cheng Quincy Teng Satori A. Marchitti Caleb M. Dillingham John F. Kenneke 《Chirality》2016,28(9):633-641
Enantiomers of chiral molecules commonly exhibit differing pharmacokinetics and toxicities, which can introduce significant uncertainty when evaluating biological and environmental fates and potential risks to humans and the environment. However, racemization (the irreversible transformation of one enantiomer into the racemic mixture) and enantiomerization (the reversible conversion of one enantiomer into the other) are poorly understood. To better understand these processes, we investigated the chiral fungicide, triadimefon, which undergoes racemization in soils, water, and organic solvents. Nuclear magnetic resonance (NMR) and gas chromatography / mass spectrometry (GC/MS) techniques were used to measure the rates of enantiomerization and racemization, deuterium isotope effects, and activation energies for triadimefon in H2O and D2O. From these results we were able to determine that: 1) the alpha‐carbonyl carbon of triadimefon is the reaction site; 2) cleavage of the C‐H (C‐D) bond is the rate‐determining step; 3) the reaction is base‐catalyzed; and 4) the reaction likely involves a symmetrical intermediate. The B3LYP/6–311 + G** level of theory was used to compute optimized geometries, harmonic vibrational frequencies, nature population analysis, and intrinsic reaction coordinates for triadimefon in water and three racemization pathways were hypothesized. This work provides an initial step in developing predictive, structure‐based models that are needed to identify compounds of concern that may undergo racemization. Chirality 28:633–641, 2016. © 2016 Wiley Periodicals, Inc. 相似文献
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Stephen A. Murray Judith L. Morgan Coleen Kane Yashoda Sharma Caleb S. Heffner Jeffrey Lake Leah Rae Donahue 《PloS one》2010,5(8)
Background
Preterm birth is an enormous public health problem, affecting over 12% of live births and costing over $26 billion in the United States alone. The causes are complex, but twin studies support the role of genetics in determining gestation length. Despite widespread use of the mouse in studies of the genetics of preterm birth, there have been few studies that actually address the precise natural gestation length of the mouse, and to what degree the timing of labor and birth is genetically determined.Methodology/Principal Findings
To further develop the mouse as a genetic model of preterm birth, we developed a high-throughput monitoring system and measured the gestation length in 15 inbred strains. Our results show an unexpectedly wide variation in overall gestation length between strains that approaches two full days, while intra-strain variation is quite low. Although litter size shows a strong inverse correlation with gestation length, genetic difference alone accounts for a significant portion of the variation. In addition, ovarian transplant experiments support a primary role of maternal genetics in the determination of gestation length. Preliminary analysis of gestation length in the C57BL/6J-Chr#A/J/NaJ chromosome substitution strain (B.A CSS) panel suggests complex genetic control of gestation length.Conclusions/Significance
Together, these data support the role of genetics in regulating gestation length and present the mouse as an important tool for the discovery of genes governing preterm birth. 相似文献93.
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The use of model organisms as tools for the investigation of human genetic variation has significantly and rapidly advanced our understanding of the aetiologies underlying hereditary traits. However, while equivalences in the DNA sequence of two species may be readily inferred through evolutionary models, the identification of equivalence in the phenotypic consequences resulting from comparable genetic variation is far from straightforward, limiting the value of the modelling paradigm. In this review, we provide an overview of the emerging statistical and computational approaches to objectively identify phenotypic equivalence between human and model organisms with examples from the vertebrate models, mouse and zebrafish. Firstly, we discuss enrichment approaches, which deem the most frequent phenotype among the orthologues of a set of genes associated with a common human phenotype as the orthologous phenotype, or phenolog, in the model species. Secondly, we introduce and discuss computational reasoning approaches to identify phenotypic equivalences made possible through the development of intra- and interspecies ontologies. Finally, we consider the particular challenges involved in modelling neuropsychiatric disorders, which illustrate many of the remaining difficulties in developing comprehensive and unequivocal interspecies phenotype mappings. 相似文献
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Caleb P. Roberts Victoria M. Donovan Carissa L. Wonkka Larkin A. Powell Craig R. Allen David G. Angeler David A. Wedin Dirac Twidwell 《Ecology and evolution》2019,9(4):1869-1879
Disturbance legacies structure communities and ecological memory, but due to increasing changes in disturbance regimes, it is becoming more difficult to characterize disturbance legacies or determine how long they persist. We sought to quantify the characteristics and persistence of material legacies (e.g., biotic residuals of disturbance) that arise from variation in fire severity in an eastern ponderosa pine forest in North America. We compared forest stand structure and understory woody plant and bird community composition and species richness across unburned, low‐, moderate‐, and high‐severity burn patches in a 27‐year‐old mixed‐severity wildfire that had received minimal post‐fire management. We identified distinct tree densities (high: 14.3 ± 7.4 trees per ha, moderate: 22.3 ± 12.6, low: 135.3 ± 57.1, unburned: 907.9 ± 246.2) and coarse woody debris cover (high: 8.5 ± 1.6% cover per 30 m transect, moderate: 4.3 ± 0.7, low: 2.3 ± 0.6, unburned: 1.0 ± 0.4) among burn severities. Understory woody plant communities differed between high‐severity patches, moderate‐ and low‐severity patches, and unburned patches (all p < 0.05). Bird communities differed between high‐ and moderate‐severity patches, low‐severity patches, and unburned patches (all p < 0.05). Bird species richness varied across burn severities: low‐severity patches had the highest (5.29 ± 1.44) and high‐severity patches had the lowest (2.87 ± 0.72). Understory woody plant richness was highest in unburned (5.93 ± 1.10) and high‐severity (5.07 ± 1.17) patches, and it was lower in moderate‐ (3.43 ± 1.17) and low‐severity (3.43 ± 1.06) patches. We show material fire legacies persisted decades after the mixed‐severity wildfire in eastern ponderosa forest, fostering distinct structures, communities, and species in burned versus unburned patches and across fire severities. At a patch scale, eastern and western ponderosa system responses to mixed‐severity fires were consistent. 相似文献
97.
Lijiang Ma Yavuz Bayram Heather M. McLaughlin Megan T. Cho Alyson Krokosky Clesson E. Turner Kristin Lindstrom Caleb P. Bupp Katey Mayberry Weiyi Mu Joann Bodurtha Veronique Weinstein Neda Zadeh Wendy Alcaraz Zöe Powis Yunru Shao Daryl A. Scott Andrea M. Lewis Janson J. White Shalani N. Jhangiani Elif Yilmaz Gulec Seema R. Lalani James R. Lupski Kyle Retterer Rhonda E. Schnur Ingrid M. Wentzensen Sherri Bale Wendy K. Chung 《Human genetics》2016,135(12):1399-1409
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Bejan J. Saeedi Daniel J. Kao David A. Kitzenberg Evgenia Dobrinskikh Kayla D. Schwisow Joanne C. Masterson Agnieszka A. Kendrick Caleb J. Kelly Amanda J. Bayless Douglas J. Kominsky Eric L. Campbell Kristine A. Kuhn Glenn T. Furuta Sean P. Colgan Louise E. Glover 《Molecular biology of the cell》2015,26(12):2252-2262