Wildlife impacts and vulnerable livelihoods in a transfrontier conservation landscape.

Interactions between humans and wildlife resulting in negative impacts are among the most pressing conservation challenges globally. In regions of smallholder livestock and crop production, interactions with wildlife can compromise human well-being and motivate negative sentiment and retaliation toward wildlife, undermining conservation goals. Although impacts may be unavoidable when human and wildlife land use overlap, scant large-scale human data exist quantifying the direct costs of wildlife to livelihoods. In a landscape of global importance for wildlife conservation in southern Africa, we quantified costs for people living with wildlife through a fundamental measure of human well-being, food security, and we tested whether existing livelihood strategies buffer certain households against crop depredation by wildlife, predominantly elephants. To do this, we estimated Bayesian multilevel statistical models based on multicounty household data (n = 711) and interpreted model results in the context of spatial data from participatory land-use mapping. Reported crop depredation by wildlife was widespread. Over half of the sample households were affected and household food security was reduced significantly (odds ratio 0.37 [0.22, 0.63]). The most food insecure households relied on gathered food sources and welfare programs. In the event of crop depredation by wildlife, these 2 livelihood sources buffered or reduced harmful effects of depredation. The presence of buffering strategies suggests a targeted compensation strategy could benefit the region's most vulnerable people. Such strategies should be combined with dynamic and spatially explicit land-use planning that may reduce the frequency of negative human-wildlife impacts. Quantifying and mitigating the human costs from wildlife are necessary steps in working toward human-wildlife coexistence.

Impactos de la Fauna y Medios de Subsistencia Vulnerables en unkl Paisaje de Conservación Transfronteriza Resumen Las interacciones entre los humanos y la fauna que resultan en impactos negativos se encuentran entre los desafíos más apremiantes para la conservación a nivel mundial. En las regiones de ganaderos y agricultores minifundistas, las interacciones con la fauna pueden poner en peligro el bienestar humano y motivar sentimientos negativos y represalias hacia la fauna, lo que debilita los objetivos de conservación. Aunque los impactos pueden evitarse cuando el uso de suelo por humanos y fauna se traslapa, existen pocos datos humanos a gran escala que cuantifiquen el costo directo de la fauna para los medios de subsistencia. Cuantificamos el costo para las personas que conviven con animales silvestres en un paisaje de importancia global para la conservación de fauna en el sur de África. La cuantificación fue realizada por medio de una medida fundamental de bienestar humano y seguridad alimentaria, y probamos si las estrategias existentes de subsistencia amortiguan a ciertos hogares ante la depredación de cultivos realizada por animales silvestres, predominantemente los elefantes. Para realizar esto, estimamos algunos modelos estadísticos bayesianos de niveles múltiples basados en los datos de hogares ubicados en múltiples condados (n = 711) e interpretamos los resultados de los modelos en el contexto de los datos espaciales a partir de un mapeo participativo de uso de suelo. La depredación de cultivos por animales silvestres fue reportada de manera generalizada. Más de la mitad de los hogares en la muestra estuvieron afectados y la seguridad alimenticia de los hogares se redujo significativamente (proporción de probabilidades 0.37 [0.22, 0.63]). Los hogares con la menor seguridad alimentaria dependían de fuentes de recolección de alimentos y programas de bienestar. En el evento de la depredación por fauna de los cultivos, estas dos fuentes de subsistencia amortiguaron o redujeron los efectos dañinos de la depredación. La presencia de las estrategias de amortiguamiento sugiere que una estrategia de compensación enfocada podría beneficiar a las personas más vulnerables de la región. Dichas estrategias deberían estar combinadas con la planeación del uso de suelo dinámica y espacialmente explícita, la cual podría reducir la frecuencia de los impactos negativos entre los humanos y la fauna. La cuantificación y mitificación del costo humano a partir de la fauna son pasos necesarios en el camino hacia la coexistencia entre los humanos y la fauna.

Positive feedback between chironomids and algae creates net mutualism between benthic primary consumers and producers.

The chironomids of Lake Mývatn show extreme population fluctuations that affect most aspects of the lake ecosystem. During periods of high chironomid densities, chironomid larvae comprise over 90% of aquatic secondary production. Here, we show that chironomid larvae substantially stimulate benthic gross primary production (GPP) and net primary production (NPP), despite consuming benthic algae. Benthic GPP in experimental mesocosms with 140,000 larvae/m2 was 71% higher than in mesocosms with no larvae. Similarly, chlorophyll a concentrations in mesocosms increased significantly over the range of larval densities. Furthermore, larvae showed increased growth rates at higher densities, possibly due to greater benthic algal availability in these treatments. We investigated the hypothesis that larvae promote benthic algal growth by alleviating nutrient limitation, and found that (1) larvae have the potential to cycle the entire yearly external loadings of nitrogen and phosphorus during the growing season, and (2) chlorophyll a concentrations were significantly greater in close proximity to larvae (on larval tubes). The positive feedback between chironomid larvae and benthic algae generated a net mutualism between the primary consumer and primary producer trophic levels in the benthic ecosystem. Thus, our results give an example in which unexpected positive feedbacks can lead to both high primary and high secondary production.

Conformational preferences of 3-(dimethylazinoyl)propanoic acid as a function of pH and solvent; intermolecular versus intramolecular hydrogen bonding.

The conformational equilibrium of 3-(dimethylazinoyl)propanoic acid (DMAPA, azinoyl = N(+)(O(-)) has a weak pH-dependence in D(2)O, with a slight preference for trans in alkaline solutions. The acid ionization constants of the protonated amine oxide and carboxylic functional groups as determined by NMR spectroscopy were 7.9 x 10(-4) and 6.3 x 10(-6), respectively. The corresponding value of K(1)/K(2) of 1.3 x 10(2) is not deemed large enough to provide experimental NMR evidence for a significant degree of intramolecular hydrogen bonding in D(2)O. Conformational preferences of DMAPA are mostly close to statistical (gauche/trans = 2/1) in other protic solvents, e.g., alcohols. However, the un-ionized form of DMAPA appears to be strongly intramolecularly hydrogen-bonded and gauche in aprotic solvents.

Determination of the dihedral angle of the monoanion of succinic acid in aprotic media.

A value of 74(+/-4) degrees was determined from NMR-observed dipolar couplings for the rotational dihedral angle of the monosuccinate anion in an aprotic liquid-crystal solution of the gauche conformation of tetraoctylammonium monosuccinate. This value is in reasonable agreement with other, somewhat less definitive, evidence gleaned from isotropic vicinal proton-proton couplings of the essentially completely gauche preference of the monosuccinate anion in tert-butyl alcohol and aprotic solvents, such as DMSO and THF, and quantum computations for the monoanion in THF.

Conformational analyses of 2,3-dihydroxypropanoic acid as a function of solvent and ionization state as determined by NMR spectroscopy.

Vicinal (1)H--(1)H coupling constants were used to determine the conformational preferences of 2,3-dihydroxypropanoic acid (1) (DL-glyceric acid) in various solvents and its different carboxyl ionization states. The stereospecific assignments of J(12) and J(13) were confirmed through the point-group substitution of the C-3 hydrogen with deuterium, yielding rac-(2SR,3RS)-[3-(2)H]-1, and the observation of only J(13) in the (1)H NMR spectra. While hydrogen bonding and steric strain may be expected to drive the conformational equilibrium, their role is overshadowed by a profound gauche effect between the vicinal hydroxyl groups that mimics other substituted ethanes, such as 1,2-ethanediol and 1,2-difluoroethane. At low pH, the conformational equilibrium is heavily weighted toward the gauche-hydroxyl rotamers with a range of 81% in DMSO-d(6) to 92% in tert-butyl alcohol-d(10). At high pH, the equilibrium exhibits a larger dependence upon the polarity and solvating capability of the medium, although the gauche effect still dominates in D(2)O, 1,4-dioxane-d(8), methanol-d(4), and ethanol-d(6) (96, 89, 85, and 83% gauche-hydroxyls respectively). The observed preference for the gauche-hydroxyl rotamers is believed to stem primarily from hyperconjugative sigma(C--H) --> sigma*(C--OH) interactions.

An NMR investigation of the importance of intramolecular hydrogen bonding in determining the conformational equilibrium of ethylene glycol in solution.

Although conformational analysis by NMR of ethylene glycol indicates generally strong preferences for the gauche conformation in solvents ranging from water to chloroform, the bulk of the NMR evidence indicates that intramolecular hydrogen bonding between the hydroxyl groups is unlikely to be a significant factor in determining that preference, except possibly in fairly non-polar solvents. The 'gauche effect' is clearly very important, especially in aqueous solution.

Intramolecular hydrogen bonding in disubstituted ethanes. A comparison of NH...O- and OH...O- Hydrogen bonding through conformational analysis of 4-amino-4-oxobutanoate (succinamate) and monohydrogen 1,4-butanoate (monohydrogen succinate) anions.

Relative strengths of amide NH...O- and carboxyl OH...O- hydrogen bonds were investigated via conformational analysis of succinamate and monohydrogen succinate anions with the aid of vicinal proton-proton NMR couplings and B3LYP DFT quantum mechanical calculations for a variety of solvents. New experimental results for succinamate are compared with those obtained from previous studies of monohydrogen succinate. While some computational results for monohydrogen succinate were published previously, the results contained herein are the product of a more powerful methodology than that used earlier. The experimental results clearly show that intramolecular hydrogen-bond formation is more favored in aprotic solvents than in protic solvents for both molecules. Furthermore, the preference of the succinate monoanion for the gauche conformation is much stronger in aprotic solvents than that of succinamate, indicating that the OH...O- hydrogen bond is substantially stronger than its NH...O- counterpart, despite the approximately 5 kcal cost for formation of the E configuration of the carboxyl group needed to make an intramolecular hydrogen bond. The actual energy differences between formation of internal hydrogen bonds for monohydrogen succinate and succinamate anion were estimated by comparison of the relative values of K1 of the respective acids in water and DMSO by a procedure first developed by Westheimer. Recent theoretical work with succinamate highlights the necessity of considering substituent orientational degrees of freedom to understand the conformational equilibria of the central CH2-CH2 torsions in disubstituted ethanes. Similar methodology is applied here to succinic acid monoanion, by mapping potential-energy surfaces with respect to the CH2-CH2 torsional, carboxyl-substituent rotational, and carboxyl-proton E/Z isomeric degrees of freedom. Boltzmann populations were compared with gauche populations estimated from the experimentally determined coupling constants. The quantum mechanical results for succinamate show a much weaker tendency toward hydrogen bonding than for the succinic acid monoanion. However, the theoretical methods employed appear to substantially overestimate contributions from intramolecularly hydrogen-bonded structures for the succinic acid monoanion when compared with experimental results. Natural bond orbital analysis, applied to the quantum mechanical wave functions of fully optimized gauche and trans structures, showed a strong correlation between the population of amide sigma*(N-H) and carboxyl sigma*(O-H) antibonding orbitals and apparent hydrogen-bonding behavior.

Dendrimeric organochalcogen catalysts for the activation of hydrogen peroxide: origins of the "dendrimer effect" with catalysts terminating in phenylseleno groups.

Several scenarios were evaluated to explain the large "dendrimer effect" observed in the bromination of cyclohexene with H(2)O(2) and NaBr catalyzed by the addition of Frechét-type dendrimers terminating in -O(CH(2))(3)SePh groups. Although phenylseleninic acid was an efficient catalyst for the oxidation of NaBr with H(2)O(2), first-order rate constants for the selenoxide elimination were too small to produce PhSeO(2)H at a rate sufficient to explain the rates of catalysis and no dendrimer effect was observed in the rates of selenoxide elimination. An induction period was observed using 1-SePh as a catalyst for the oxidation of Br(-) with H(2)O(2). The addition of preformed selenoxide 1-Se(=O)Ph gave immediate catalysis with no induction period. However, rates of oxidation of the selenides with H(2)O(2) under homogeneous or biphasic conditions or with t-BuOOH under homogeneous conditions were too slow to account for the rates of catalysis, and no dendrimer effect was observed in the rates of oxidation. The primary oxidant for converting selenides to selenoxides was "Br(+)" produced initially by the uncatalyzed background reaction of H(2)O(2) with NaBr and then produced catalytically following formation of selenoxide groups. Autocatalysis is observed, and the rate of oxidation increases with the number of SePh groups. Autocatalysis is the source of the large dendrimer effect observed with the SePh series of catalysts.