RESUMEN
AIM: To observe the variation in accumulation of Fusarium and Alternaria mycotoxins across a topographically heterogeneous field and tested biotic (fungal and bacterial abundance) and abiotic (microclimate) parameters as explanatory variables. METHODS AND RESULTS: We selected a wheat field characterized by a diversified topography, to be responsible for variations in productivity and in canopy-driven microclimate. Fusarium and Alternaria mycotoxins where quantified in wheat ears at three sampling dates between flowering and harvest at 40 points. Tenuazonic acid (TeA), alternariol (AOH), alternariol monomethyl ether (AME), tentoxin (TEN), deoxynivalenol (DON), zearalenone (ZEN) and deoxynivalenol-3-Glucoside (DON.3G) were quantified. In canopy temperature, air and soil humidity were recorded for each point with data-loggers. Fusarium spp. as trichothecene producers, Alternaria spp. and fungal abundances were assessed using qPCR. Pseudomonas fluorescens bacteria were quantified with a culture based method. We only found DON, DON.3G, TeA and TEN to be ubiquitous across the whole field, while AME, AOH and ZEN were only occasionally detected. Fusarium was more abundant in spots with high soil humidity, while Alternaria in warmer and drier spots. Mycotoxins correlated differently to the observed explanatory variables: positive correlations between DON accumulation, tri 5 gene and Fusarium abundance were clearly detected. The correlations among the others observed variables, such as microclimatic conditions, varied among the sampling dates. The results of statistical model identification do not exclude that species coexistence could influence mycotoxin production. CONCLUSIONS: Fusarium and Alternaria mycotoxins accumulation varies heavily across the field and the sampling dates, providing the realism of landscape-scale studies. Mycotoxin concentrations appear to be partially explained by biotic and abiotic variables. SIGNIFICANCE AND IMPACT OF THE STUDY: We provide a useful experimental design and useful data for understanding the dynamics of mycotoxin biosynthesis in wheat.
Asunto(s)
Contaminación de Alimentos/análisis , Micotoxinas/química , Triticum/química , Alternaria/genética , Alternaria/crecimiento & desarrollo , Alternaria/metabolismo , Fusarium/genética , Fusarium/crecimiento & desarrollo , Fusarium/metabolismo , Glucósidos/análisis , Glucósidos/metabolismo , Lactonas/análisis , Lactonas/metabolismo , Microclima , Micotoxinas/metabolismo , Pseudomonas fluorescens/química , Pseudomonas fluorescens/genética , Pseudomonas fluorescens/crecimiento & desarrollo , Pseudomonas fluorescens/metabolismo , Metabolismo Secundario , Microbiología del Suelo , Ácido Tenuazónico/análisis , Ácido Tenuazónico/metabolismo , Tricotecenos/análisis , Tricotecenos/metabolismo , Triticum/microbiología , Zearalenona/análisis , Zearalenona/metabolismoRESUMEN
Valence and dipole-bound negative ions of the nitroethane (NE) molecule and its clusters are studied using photoelectron spectroscopy (PES), Rydberg electron transfer (RET) techniques, and ab initio methods. Valence adiabatic electron affinities (EA(a)s) of NE, C(2)H(5)NO(2), and its clusters, (C(2)H(5)NO(2))(n), n=2-5, are estimated using vibrationally unresolved PES to be 0.3+/-0.2 eV (n=1), 0.9+/-0.2 eV (n=2), 1.5+/-0.2 eV (n=3), 1.9+/-0.2 eV (n=4), and 2.1+/-0.2 eV (n=5). These energies were then used to determine stepwise anion-neutral solvation energies and compared with previous literature values. Vertical detachment energies for (C(2)H(5)NO(2))(n)(-) were also measured to be 0.92+/-0.10 eV (n=1), 1.63+/-0.10 eV (n=2), 2.04+/-0.10 eV (n=3), and 2.3+/-0.1 eV (n=4). RET experiments show that Rydberg electrons can be attached to NE both as dipole-bound and valence bound anion states. The results are similar to those found for nitromethane (NM), where it was argued that the diffuse dipole state act as a "doorway state" to the more tightly bound valence anion. Using previous models for relating the maximum in the RET dependence of the Rydberg effective principle number n(max)(*), the dipole-bound electron affinity is predicted to be approximately 25 meV. However, a close examination of the RET cross section data for NE and a re-examination of such data for NM finds a much broader dependence on n(*) than is seen for RET in conventional dipole bound states and, more importantly, a pronounced [l] dependence is found in n(max)(*) (n(max)(*) increases with [l]). Ab initio calculations agree well with the experimental results apart from the vertical electron affinity value associated with the dipole bound state which is predicted to be 8 meV. Moreover, the calculations help to visualize the dramatic difference in the distributions of the excess electron for dipole-bound and valence states, and suggest that NE clusters form only anions where the excess electron localizes on a single monomer.
Asunto(s)
Etano/análogos & derivados , Nitroparafinas/química , Algoritmos , Transporte de Electrón , Electrones , Etano/química , Metano/análogos & derivados , Metano/química , Modelos Moleculares , Conformación Molecular , Nitrobencenos/química , Teoría Cuántica , Solventes/química , TermodinámicaRESUMEN
The interatomic Coulombic decay (ICD) in the Ne dimer is discussed in view of the recent experimental results. The ICD electron spectrum and the kinetic energy release of the Ne+ fragments resulting after Coulomb explosion of Ne2 (2+) are computed and compared to the measured ones. A very good agreement is found, confirming the dynamics predicted for this decay mechanism. The effect of the temperature on the electron spectrum is briefly investigated.
RESUMEN
Dissociative electron attachment to 5-chlorouracil cannot proceed directly , since the dissociative σ* state is too short-lived and autodetachment occurs rapidly. Effcient fragmentation of the chlorouracil anion radical is only possible if a nondissociative π* state is formed initially that undergoes an intersection with the σ* state at an elongated C-Cl distance.
Asunto(s)
Uracilo/análogos & derivados , Aniones/química , Electrones , Termodinámica , Uracilo/químicaRESUMEN
Metastable states of O (2-), S (2-), B (2-), and Al (2-) are studied in the framework of the complex absorbing potential method using highly correlated multireference configuration interaction wave functions. The first row species O (2-) and B (2-) are found to be broad resonances showing widths of roughly 1.7 eV, whereas the second row systems S (2-) and Al (2-) possess widths clearly smaller than 1 eV. The identified resonance states are compared to the fundamental H (2-) resonance, and the relationship with recent electron scattering experiments is discussed.