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  • 1
    ISSN: 0040-4020
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1573-4927
    Keywords: nonelectrophoretic structural variability ; Drosophila melanogaster ; phosphoglucomutase ; genetic polymorphism ; heat denaturation study
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract A simple procedure is described to detect genetic heterogeneity within electrophoretic classes at a locus in Drosophila, based on electrophoresis and heat denaturation studies. Temperature-resistant (tr) and temperature-sensitive (ts) isoelectrophoretic alleles at the phosphoglucomutase locus (Pgm) are present at polymorphic frequencies in natural and in laboratory populations of Drosophila melanogaster.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0947-6539
    Keywords: allylic alcohols ; gas-phase chemistry ; ions ; mechanistic studies ; nucleophilic substitutions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A first demonstration of the existence of the concerted SN2′ mechanism in the gas phase was obtained by establishing the regioselectivity of the attack of a neutral nucleophile, such as MeOH, on several allylic oxonium ions. These were generated in the gas phase by the reaction of radiolytically formed GA+ acids (GA+=CnH+5 (n = 1, 2), iC3H+7, and (CH3)2F+) with trans- (1) and cis-2-buten-1-ol (2) as well as with 1-buten-3-ol (3). Firm evidence in favor of the concerted SN2′ pathway accompanying the classical SN2 one in these systems was obtained after careful evaluation of the extent of conceivable intramolecular isomerization both of the primary oxonium ions from GA+ attack on 1-3 before nucleophilic displacement by MeOH and of their substituted intermediates before neutralization. The intermediacy of free allylic ions in the nucleophilic substitution was ruled out by generating the ions by protonation of 1,3-butadiene and by investigating their behavior in exactly the same media employed in the substitution reactions. The regioselectivity of MeOH with the ionic substrates investigated showed the occurrence of nearly equally extensive SN2′ and SN2 pathways in the oxonium ions from 1 (SN2′ (57 ± 2%) and SN2 (43 ± 2%)) and 3 (SN2′ (54 ± 2%) and SN2 (46 ± 2%)), whereas, with 2, the SN2 (66 ± 2%) reaction prevailed over the SN2′ one (34 ± 2%). The role of intrinsic structural factors in determining the SN2′/SN2 branching in the selected oxonium ions is discussed.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0947-6539
    Keywords: cyclohexenols ; elimination reactions ; gas-phase chemistry ; mechanistic studies ; nucleophilic substitutions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Our radiolytic study of the occurrence in the gas phase of concerted SN2′ reactions on several open-chain allylic oxonium ions generated in the gas phase from the attack of gaseous GA+ acids (GA+=CnH+5 (n = 1, 2), iC3H+7, and (CH3)2F+) on suitable substrates is now continued with cyclic allylic alcohols, such as 3-methyl-2-cyclohexen-1-ol (1) and 1-methyl-2-cyclohexen-1-ol (2), with both MeOH and NMe3 as neutral nucleophiles. With MeOH as the nucleophile, the substitution reaction exclusively takes place on 1 as the starting compounds, whereas when the substrate is 2 it is accompanied by extensive elimination. With NMe3, only the elimination reaction is observed in the same systems. The analysis of the isomeric distribution of the substitution and elimination products allows definition of the corresponding reaction patterns. As for open-chain oxonium ions, the nucleophilic attack on O-protonated 1 and 2 is preceded by significant intramolecular interconversion. Partial unimolecular dissociation of the same ionic intermediates also takes place. After careful evaluation of the extent of these side processes, it is demonstrated that the O-protonated 1 undergoes the concerted SN2 process with MeOH almost exclusively (≥ 99%). With O-protonated 2, how ever, the concerted SN2′ pathway (84-95%) prevails over the classical SN2 one (6-17%). Concomitant [1,2] (E2) and [1,4] elimination (E2′) pathways involve attack of the selected nucleophiles on the oxonium ions from 1 and 2. Their relative extent (E2′/E2:1.78-1.96 (1); 1.43-1 70 (2)) appears only slightly dependent on the nature of the ionic substrate, the nucleophile (whether MeOH or NMe3), and the leaving group (whether H2O or MeOH). The effects of both intrinsic structural factors and experimental conditions in determining the SN2′/SN2 and E2′/E2 branchings in the selected oxonium ions is discussed and compared with related gas-phase data.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Publication Date: 2018
    Description: We show that current optimization and empirical methods to determine stomatal conductance in Earth system models (ESMs) yield similar results and exhibit similar species‐specific sensitivities to environmental variables, including CO2. Failure to account for different stomatal sensitivities across species or vegetation types will lead to significant errors in ESM simulations, particularly for terrestrial water fluxes. The key fitted parameter calibrating optimization or empirical stomatal conductance models to different global vegetation types may be determined from mean annual precipitation, as shown here for the empirical Ball‐Berry slope, overcoming constraints imposed by inflexibilities in current global calibration methods. Abstract Earth system models (ESMs) rely on the calculation of canopy conductance in land surface models (LSMs) to quantify the partitioning of land surface energy, water, and CO2 fluxes. This is achieved by scaling stomatal conductance, gw, determined from physiological models developed for leaves. Traditionally, models for gw have been semi‐empirical, combining physiological functions with empirically determined calibration constants. More recently, optimization theory has been applied to model gw in LSMs under the premise that it has a stronger grounding in physiological theory and might ultimately lead to improved predictive accuracy. However, this premise has not been thoroughly tested. Using original field data from contrasting forest systems, we compare a widely used empirical type and a more recently developed optimization‐type gw model, termed BB and MED, respectively. Overall, we find no difference between the two models when used to simulate gw from photosynthesis data, or leaf gas exchange from a coupled photosynthesis‐conductance model, or gross primary productivity and evapotranspiration for a FLUXNET tower site with the CLM5 community LSM. Field measurements reveal that the key fitted parameters for BB and MED, g1B and g1M, exhibit strong species specificity in magnitude and sensitivity to CO2, and CLM5 simulations reveal that failure to include this sensitivity can result in significant overestimates of evapotranspiration for high‐CO2 scenarios. Further, we show that g1B and g1M can be determined from mean ci/ca (ratio of leaf intercellular to ambient CO2 concentration). Applying this relationship with ci/ca values derived from a leaf δ13C database, we obtain a global distribution of g1B and g1M, and these values correlate significantly with mean annual precipitation. This provides a new methodology for global parameterization of the BB and MED models in LSMs, tied directly to leaf physiology but unconstrained by spatial boundaries separating designated biomes or plant functional types.
    Print ISSN: 1354-1013
    Electronic ISSN: 1365-2486
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Geography
    Published by Wiley
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  • 6
    Publication Date: 2015-10-14
    Description: Earth System Models (ESMs) typically use static responses to temperature to calculate photosynthesis and respiration, but experimental evidence suggests that many plants acclimate to prevailing temperatures. We incorporated representations of photosynthetic and leaf respiratory temperature acclimation into the Community Land Model (CLM), the terrestrial component of the Community Earth System Model. These processes increased terrestrial carbon pools by 20 Pg C (22%) at the end of the twenty-first century under a business-as-usual (RCP8.5) climate scenario. Including the less certain estimates of stem and root respiration acclimation increased terrestrial carbon pools by an additional 17 Pg C (~40% overall increase). High latitudes gained the most carbon with acclimation, and tropical carbon pools increased least. However, results from both of these regions remain uncertain; few relevant data exist for tropical and boreal plants or for extreme temperatures. Constraining these uncertainties will produce more realistic estimates of land-carbon feedbacks throughout the twenty-first century.
    Print ISSN: 0094-8276
    Electronic ISSN: 1944-8007
    Topics: Geosciences , Physics
    Published by Wiley on behalf of American Geophysical Union (AGU).
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  • 7
    Publication Date: 2016-02-27
    Description: Climate control on global vegetation productivity patterns has intensified in response to recent global warming. Yet, the contributions of the leading internal climatic variations to global vegetation productivity are poorly understood. Here we use 30 years of global satellite observations to study climatic variations controls on continental and global vegetation productivity patterns. El Niño-Southern Oscillation (ENSO) phases (La Niña, neutral, and El Niño years) appear to be a weaker control on global-scale vegetation productivity than previously thought, although continental-scale responses are substantial. There is also clear evidence that other non-ENSO climatic variations have a strong control on spatial patterns of vegetation productivity mainly through their influence on temperature. Among the eight leading internal climatic variations, the East Atlantic/West Russia Pattern extensively controls the ensuing year vegetation productivity of the most productive tropical and temperate forest ecosystems of the Earth's vegetated surface through directionally consistent influence on vegetation greenness. The Community Climate System Model (CCSM4) simulations do not capture the observed patterns of vegetation productivity responses to internal climatic variations. Our analyses show the ubiquitous control of climatic variations on vegetation productivity and can further guide CCSM and other Earth system models developments to represent vegetation response patterns to unforced variability. Several winter time internal climatic variation indices show strong potentials on predicting growing season vegetation productivity two to six seasons ahead which enables national governments and farmers forecast crop yield to ensure supplies of affordable food, famine early warning, and plan management options to minimize yield losses ahead of time. This article is protected by copyright. All rights reserved.
    Print ISSN: 1354-1013
    Electronic ISSN: 1365-2486
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Geography
    Published by Wiley
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  • 8
    Publication Date: 2019
    Description: 〈p〉Atmospheric vapor pressure deficit (VPD) is a critical variable in determining plant photosynthesis. Synthesis of four global climate datasets reveals a sharp increase of VPD after the late 1990s. In response, the vegetation greening trend indicated by a satellite-derived vegetation index (GIMMS3g), which was evident before the late 1990s, was subsequently stalled or reversed. Terrestrial gross primary production derived from two satellite-based models (revised EC-LUE and MODIS) exhibits persistent and widespread decreases after the late 1990s due to increased VPD, which offset the positive CO〈sub〉2〈/sub〉 fertilization effect. Six Earth system models have consistently projected continuous increases of VPD throughout the current century. Our results highlight that the impacts of VPD on vegetation growth should be adequately considered to assess ecosystem responses to future climate conditions.〈/p〉
    Electronic ISSN: 2375-2548
    Topics: Natural Sciences in General
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  • 9
    Publication Date: 2019
    Description: Abstract Land models are often used to simulate terrestrial responses to future environmental changes, but these models are not commonly evaluated with data from experimental manipulations. Results from experimental manipulations can identify and evaluate model assumptions that are consistent with appropriate ecosystem responses to future environmental change. We conducted simulations using three coupled carbon‐nitrogen versions of the Community Land Model (CLM, versions 4, 4.5 and‐ the newly developed‐ 5), and compared the simulated response to nitrogen (N) and atmospheric carbon dioxide (CO2) enrichment with meta‐analyses of observations from similar experimental manipulations. In control simulations, successive versions of CLM showed a poleward increase in gross primary productivity and an overall bias reduction, compared to FLUXNET‐MTE observations. Simulations with N and CO2 enrichment demonstrate that CLM transitioned from a model that exhibited strong nitrogen limitation of the terrestrial carbon cycle (CLM4) to a model that showed greater responsiveness to elevated concentrations of CO2 in the atmosphere (CLM5). Overall, CLM5 simulations showed better agreement with observed ecosystem responses to experimental N and CO2 enrichment than previous versions of the model. These simulations also exposed shortcomings in structural assumptions and parameterizations. Specifically, no version of CLM captures changes in plant physiology, allocation, and nutrient uptake that are likely important aspects of terrestrial ecosystems’ responses to environmental change. These highlight priority areas that should be addressed in future model developments. Moving forward, incorporating results from experimental manipulations into model benchmarking tools that are used to evaluate model performance will help increase confidence in terrestrial carbon cycle projections.
    Print ISSN: 0886-6236
    Electronic ISSN: 1944-9224
    Topics: Biology , Chemistry and Pharmacology , Geography , Geosciences , Physics
    Published by Wiley on behalf of American Geophysical Union (AGU).
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  • 10
    Publication Date: 2019
    Description: Abstract The divergence among Earth system models in the terrestrial carbon cycle has prompted interest in how to reduce uncertainty. Previous studies have identified model structural uncertainty arising from process parameterizations and parameter values. The current study highlights the importance of climate forcing in generating carbon cycle uncertainty. We use simulations in which three models (CLM4, CLM4.5, CLM5) with substantially different carbon cycles are forced with two climate reconstructions (CRUNCEPv7, GSWP3v1) to examine the contributions of model structure and climate to uncertainty in the carbon cycle over the period 1850–2014. Climate uncertainty for global annual net biome production exceeds one‐third of total uncertainty (defined as the sum of climate and model structure uncertainty) in the first half of the twentieth century, but declines after the 1950s. Global annual gross primary productivity, net primary productivity, heterotrophic respiration, and vegetation and soil carbon stocks have substantial climate uncertainty (relative to total uncertainty) throughout the simulation period. Climate forcing contributes more than one‐half of total uncertainty for these carbon cycle fluxes and stocks throughout boreal North America and Eurasia, some mid‐latitude regions, and in eastern Amazonia and western equatorial Africa during the decade 2000–2009. Comparison with observationally‐based datasets of the carbon cycle using model benchmarking methods provides insight into strengths and deficiencies among models and climate forcings, but we caution against overreliance on benchmarking to discriminate among models. The conceptualization of uncertainty arising from this study implies embracing multiple feasible model simulations rather than focusing on which model or simulation is best.
    Print ISSN: 0886-6236
    Electronic ISSN: 1944-9224
    Topics: Biology , Chemistry and Pharmacology , Geography , Geosciences , Physics
    Published by Wiley on behalf of American Geophysical Union (AGU).
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