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Rivers and streams contribute to global carbon cycling by decomposing immense quantities of terrestrial plant matter. However, decomposition rates are highly variable and large-scale patterns and drivers of this process remain poorly understood. Using a cellulose-based assay to reflect the primary constituent of plant detritus, we generated a predictive model (81% variance explained) for cellulose decomposition rates across 514 globally distributed streams. A large number of variables were important for predicting decomposition, highlighting the complexity of this process at the global scale. Predicted cellulose decomposition rates, when combined with genus-level litter quality attributes, explain published leaf litter decomposition rates with high accuracy (70% variance explained). Our global map provides estimates of rates across vast understudied areas of Earth and reveals rapid decomposition across continental-scale areas dominated by human activities. [ABSTRACT FROM AUTHOR]

Children in everyday environments experience verbs separated by minutes or hours and linked to events that vary in their similarity. Prior studies have shown that seeing similar events can be beneficial for verb learning (e.g., complex events), but there is also evidence that varied events or seeing both similar and varied events is useful; more studies are needed. In addition, few prior verb studies have tested verb learning from spaced practice. In Study 1, 3½- and 4½-year-olds (N = 72) saw either three similar events, three varied events, or a single live event (control) while hearing a new verb; events were separated by 1-min delays. Results showed better performance in multiple-event conditions than in the single-event condition and showed more extensions with age. Specifically, children benefitted more from seeing varied events with age. In Study 2, 2½-, 3½-, and 4½-year-olds (N = 163) either saw similar and then varied events or saw all varied video events separated by 1-min delays or no delays. The youngest children performed significantly better in the similar first condition than in the all varied condition, showing the first evidence of this benefit following spaced practice. In addition, as in Study 1, performance after seeing varied events increased with age. Together, these studies show that children can compare events separated in time and that their ability to learn verbs from varied examples develops with age., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Extreme weather events, such as hurricanes, can cause ecological disturbances that alter energy and nutrients across terrestrial-aquatic boundaries. Yet, relatively few studies have considered the impacts of extreme weather events on biogeochemical dynamics in watersheds at larger spatial scales. Here, we assessed the effects of Hurricanes Harvey and Irma on the export of dissolved organic matter (DOM) and nutrients in ten watersheds from five southeastern states of the United States. We quantified the magnitude of dissolved organic carbon (DOC) and nutrients exported during the storms and assessed the changes in DOM sources and bioreactivity after storms. Our results show that the storm-mobilized DOC and nutrients fluxes were primarily driven by water discharge. The proportions of terrestrial, humic-like DOM compounds increased, and percent autochthonous, protein-like DOM decreased during high flows. Percent bioreactive DOC decreased with increasing discharge. Bioreactivity increased with increasing nitrate concentration, but decreased as percent terrestrial humic-like DOM, aromaticity, and molecular weight increased. These observations suggest that storms may have shifted flow paths to shallower depths that promoted the addition of biorefractory organic matter from topsoils into the water column. Notably, the total flux of bioreactive DOC was at least nearly twice as high at peak discharge, indicating materials transported by large storm flows could strongly enhance microbial activity in streams, although the position of storm-mediated microbial hotspots would depend on the flow rate and other instream parameters. Additionally, compared to forest-dominated watersheds, urban watersheds exported high loads of nutrients and bioreactive DOC, and a wetland-dominated watershed had a prolonged, but relatively subdued export of DOC and nutrients. Together, our findings highlight the ecological significance of extreme weather and climate events in leading to rapid, large-magnitude changes in energy and nutrient availability within drainage networks, and the potential interactions between land use and climate change on watershed biogeochemistry., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Antibiotics can be administered orally or parenterally in swine production, which may influence antimicrobial resistance (AMR) development in gut bacteria. A total of 40 barrows and 40 gilts were used to determine the effects of tylosin administration route on growth performance and fecal enterococcal AMR. The antibiotic treatments followed Food and Drug Administration label directions and were as follows: (1) no antibiotic (CON), (2) 110 mg tylosin per kg feed for 21 d (IN-FEED), (3) 8.82 mg tylosin per kg body weight through intramuscular injection twice daily for the first 3 d of each week for 3 weeks (IM), and (4) 66 mg tylosin per liter of drinking water (IN-WATER). Antibiotics were administered during d 0 to 21 and all pigs were then fed the CON diet from d 21 to 35. Fecal samples were collected on d 0, 21, and 35. Antimicrobial susceptibility was determined by microbroth dilution method. No evidence of route × sex interaction ( p  > 0.55) was observed for growth performance. From d 0 to 21, pigs receiving CON and IN-FEED had greater ( p  < 0.05) average daily gain (ADG) than those receiving IM, with the IN-WATER group showing intermediate ADG. Pigs receiving CON had greater ( p  < 0.05) gain-to-feed ratio (G:F) than IM and IN-WATER, but were not different from pigs receiving IN-FEED. Overall, enterococcal isolates collected from pigs receiving IN-FEED or IM were more resistant ( p  < 0.05) to erythromycin and tylosin than CON and IN-WATER groups. Regardless of administration route, the estimated probability of AMR to these two antibiotics was greater on d 21 and 35 than on d 0. In summary, IM tylosin decreased ADG and G:F in finishing pigs, which may be because of a response to the handling during injection administration. Tylosin administration through injection and feed resulted in greater probability of enterococcal AMR to erythromycin and tylosin compared with in-water treatment.

The design and synthesis of 10-(2-benzoxazolcarbonyl)-DDACTHF (1) as an inhibitor of glycinamide ribonucleotide transformylase (GAR Tfase) and aminoimidazole carboxamide transformylase (AICAR Tfase) are reported. Ketone 1 and the corresponding alcohol 13 were evaluated for inhibition of GAR Tfase and AICAR Tfase and the former was found to be a potent inhibitor of recombinant human (rh) GAR Tfase (Ki=600 nM).

The high-throughput synthesis and screening of compound libraries hold tremendous promise for drug discovery and powerful methods for both solid-phase and solution-phase library preparation have been introduced. The question of which approach (solution-phase versus solid-phase) is best for the preparation of chemical libraries has been replaced by which approach is most appropriate for a particular target or screen. Herein we highlight distinctions in the two approaches that might serve as useful considerations at the onset of new programs. This is followed by a more personal account of our own focus on solution-phase techniques for the preparation of libraries designed to modulate cellular signaling by targeting protein-protein or protein-DNA interactions. The screening of our libraries against a prototypical set of extracellular and intracellular targets, using a wide range of assay formats, provided the first small-molecule modulators of the protein-protein interactions studied, and a generalized approach for conducting such studies.

Three food types were analyzed for the presence of Salmonella by the AOAC culture method and by the International Organization for Standardization (ISO 6579:2002) culture method. Paired test portions of each food type were simultaneously analyzed by both methods. A total of 21 laboratories representing federal government agencies and private industry, in the United States and Europe, participated in this interlaboratory study. Foods were artificially contaminated with Salmonella and competing microflora if naturally contaminated sources were not available. No statistical differences (p < 0.05) were observed between the AOAC and ISO culture methods for fresh cheese and dried egg products. A statistically significant difference was observed for one of the 2 lots of poultry from the first trial. The poultry meat used in this run was radiation sterilized, artificially contaminated with Salmonella and competitive flora, and then lyophilized. A second trial was conducted with 2 separate lots of raw ground chicken that were naturally contaminated. The results from the second trial showed no statistical difference between the 2 culture methods. A third trial involving 4 laboratories was conducted on 2 separate lots of naturally contaminated raw poultry. Again, no statistically significant differences occurred. It is recommended that ISO 6579:2002 culture method for Salmonella be adopted Official First Action for the analysis of fresh cheese, fresh chilled and frozen poultry, and dried egg products.

The erythropoietin receptor (EPOr) is activated by ligand-induced homodimerization, which leads to the proliferation and differentiation of erythroid progenitors. Through the screening of combinatorial libraries of dimeric iminodiacetic acid diamides, novel small molecule binders of EPOr were identified in a protein binding assay. Evaluation of a series of analogues led to optimization of binding subunits, and these were utilized in the synthesis of higher order dimer, trimer, and tetramer libraries. Several of the most active EPOr binders were found to be partial agonists and induced concentration-dependent proliferation of an EPO-dependent cell line (UT-7/EPO) while having no effect on a cell line lacking the EPOr (FDC-P1). An additional compound library, based on a symmetrical isoindoline-5,6-dicarboxylic acid template and including the optimized binding subunits, was synthesized and screened leading to the identification of additional EPO mimetics.

Reaction of Mo(N[R]Ar)(3) (R = (t)Bu or C(CD(3))(2)CH(3)) with N(2)O gives rise exclusively to a 1:1 mixture of nitride NMo(N[R]Ar)(3) and nitrosyl ONMo(N[R]Ar)(3), rather than the known oxo complex OMo(N[R]Ar)(3) and dinitrogen. Solution calorimetry measurements were used to determine the heat of reaction of Mo(N[R]Ar)(3) with N(2)O and, independently, the heat of reaction of Mo(N[R]Ar)(3) with NO. Derived from the latter measurements is an estimate (155.3 +/- 3.3 kcal.mol(-1)) of the molybdenum-nitrogen bond dissociation enthalpy for the terminal nitrido complex, NMo(N[R]Ar)(3). Comparison of the new calorimetry data with those obtained previously for oxo transfer to Mo(N[R]Ar)(3) shows that the nitrous oxide N-N bond cleavage reaction is under kinetic control. Stopped-flow kinetic measurements revealed the reaction to be first order in both Mo(N[R]Ar)(3) and N(2)O, consistent with a mechanism featuring post-rate-determining dinuclear N-N bond scission, but also consistent with cleavage of the N-N bond at a single metal center in a mechanism requiring the intermediacy of nitric oxide. The new 2-adamantyl-substituted molybdenum complex Mo(N[2-Ad]Ar)(3) was synthesized and found also to split N(2)O, resulting in a 1:1 mixture of nitrosyl and nitride products; the reaction exhibited first-order kinetics and was found to be ca. 6 times slower than that for the tert-butyl-substituted derivative. Discussed in conjunction with studies of the 2-adamantyl derivative Mo(N[2-Ad]Ar)(3) is the role of ligand-imposed steric constraints on small-molecule, e.g. N(2) and N(2)O, activation reactivity. Bradley's chromium complex Cr(N(i)Pr(2))(3) was found to be competitive with Mo(N[R]Ar)(3) for NO binding, while on its own exhibiting no reaction with N(2)O. Competition experiments permitted determination of ratios of second-order rate constants for NO binding by the two molybdenum complexes and the chromium complex. Analysis of the product mixtures resulting from carrying out the N(2)O cleavage reactions with Cr(N(i)Pr(2))(3) present as an in situ NO scavenger rules out as dominant any mechanism involving the intermediacy of NO. Simplest and consistent with all the available data is a post-rate-determining bimetallic N-N scission process. Kinetic funneling of the reaction as indicated is taken to be governed by the properties of nitrous oxide as a ligand, coupled with the azophilic nature of three-coordinate molybdenum(III) complexes.

Oxidative addition of the sulfur-sulfur bond of 2,2'-pyridine disulfide (C(5)H(4)NS-SC(5)H(4)N) with L(3)W(CO)(3) [L = pyridine, (1)/(3)CHPT; CHPT = cycloheptatriene] in methylene chloride solution yields the seven-coordinate W(II) thiolate complex W(eta(2)-mp)(2)(CO)(3) (mp = monoanion of 2-mercaptopyridine). This complex undergoes slow further oxidative addition with additional pyridine disulfide, yielding W(eta(2)- mp)(4). Reaction of W(eta(2)-mp)(2)(CO)(3) with NO results in quantitative formation of the six-coordinate W(0) complex W(eta(2)-mp)(2)(NO)(2). Reaction of W(eta(2)-mp)(2)(CO)(3) with NO in the presence of added pyridine disulfide yields the seven-coordinate W(II) nitrosyl complex W(eta(2)-mp)(3)(NO) as well as W(eta(2)-mp)(2)(NO)(2) and trace amounts of W(eta(2)-mp)(4). The complex W(eta(2)-mp)(3)(NO) is formed during the course of the reaction and not by reaction of W(eta(2)-mp)(4) or W(eta(2)-mp)(2)(NO)(2) with NO under these conditions. The crystal structures of W(eta(2)- mp)(2)(CO)(3), W(eta(2)-mp)(2)(NO)(2), and W(eta(2)-mp)(3)(NO) are reported.

The p-nitrophenylcellobiosidase (PNPCase) activity of Trichoderma reesei cellobiohydrolase I (CBH I) was competitively inhibited by concentrations of guanidine hydrochloride (Gdn HCl) that did not affect the tryptophan fluorescence of this enzyme. The Km of CBH I, 3.6 mM, was increased to 45.4 mM in the presence of 0.14 M Gdn HCl, the concentration that was required to inhibit the enzyme by 50%. A similar concentration of lithium chloride and urea had little effect on the PNPCase activity of CBH I. Maximal inhibition was pH dependent, occurring in the range of pH 4.0 to 5.0, which is in the range for maximal activity. Analysis of the inhibition data indicated that 1.2 molecules of Gdn HCl combined reversibly with 1 molecule of CBH I. Other hydrolases and proteases were also inhibited by Gdn HCl. It is suggested that the inhibition of CBH I by Gdn HCl occurs as a result of the interaction between the positively charged guanidinium group of Gdn HCl and the carboxylate group of glutamic acid 126, postulated to be in the catalytic center of this enzyme.