Tricarballylic ester formation during biosynthesis of fumonisin mycotoxins in \u3ci\u3eFusarium verticillioides\u3c/i\u3e

Fumonisins are agriculturally important mycotoxins produced by the maize pathogen Fusarium verticillioides. The chemical structure of fumonisins contains two tricarballylic esters, which are rare structural moieties and important for toxicity. The mechanism for the tricarballylic ester formation is not well understood. FUM7 gene of F. verticillioides was predicted to encode a dehydrogenase/reductase, and when it was deleted, the mutant produced tetradehydro fumonisins (DH4–FB). MS and NMR analysis of DH4–FB1 indicated that the esters consist of aconitate with a 3′-alkene function, rather than a 2′-alkene function. Interestingly, the purified DH4–FB1 eventually yielded three chromatographic peaks in HPLC. However, MS revealed that the metabolites of the three peaks all had the same mass as the initial single-peak DH4–FB1. The results suggest that DH4–FB1 can undergo spontaneous isomerization, probably including both cis–trans stereoisomerization and 3′- to 2′-ene regioisomerization. In addition, when FUM7 was expressed in Escherichia coli and the resulting enzyme, Fum7p, was incubated with DH4–FB, no fumonisin with typical tricarballylic esters was formed. Instead, new fumonisin analogs that probably contained isocitrate and/or oxalosuccinate esters were formed, which reveals new insight into fumonisin biosynthesis. Together, the data provided both genetic and biochemical evidence for the mechanism of tricarballylic ester formation in fumonisin biosynthesis

Tricarballylic ester formation during biosynthesis of fumonisin mycotoxins in \u3ci\u3eFusarium verticillioides\u3c/i\u3e

Fumonisins are agriculturally important mycotoxins produced by the maize pathogen Fusarium verticillioides. The chemical structure of fumonisins contains two tricarballylic esters, which are rare structural moieties and important for toxicity. The mechanism for the tricarballylic ester formation is not well understood. FUM7 gene of F. verticillioides was predicted to encode a dehydrogenase/reductase, and when it was deleted, the mutant produced tetradehydro fumonisins (DH4–FB). MS and NMR analysis of DH4–FB1 indicated that the esters consist of aconitate with a 3′-alkene function, rather than a 2′-alkene function. Interestingly, the purified DH4–FB1 eventually yielded three chromatographic peaks in HPLC. However, MS revealed that the metabolites of the three peaks all had the same mass as the initial single-peak DH4–FB1. The results suggest that DH4–FB1 can undergo spontaneous isomerization, probably including both cis–trans stereoisomerization and 3′- to 2′-ene regioisomerization. In addition, when FUM7 was expressed in Escherichia coli and the resulting enzyme, Fum7p, was incubated with DH4–FB, no fumonisin with typical tricarballylic esters was formed. Instead, new fumonisin analogs that probably contained isocitrate and/or oxalosuccinate esters were formed, which reveals new insight into fumonisin biosynthesis. Together, the data provided both genetic and biochemical evidence for the mechanism of tricarballylic ester formation in fumonisin biosynthesis

Probing Spectral Line Gradients Beyond One Effective Radius in NGC 3610

The outer region (0.75--1.25 r_e in the B-band) of the merger-remnant elliptical NGC 3610 is studied using extremely high signal to noise Keck spectra, with a supplementary spectrum of the galaxy center. Stellar population parameters -- age, [Z/H], [$\alpha$/Fe] -- are measured in several apertures along the slit. Using the multi-index simultaneous fitting method of Proctor et al. (2004), no significant stellar population gradients are detected in the outer parts of the galaxy. The overall gradients relative to the galaxy center are consistent with those found in many other early-type galaxies, though the metallicity gradient is much steeper than would be expected if NGC 3610 formed in a major merger event. Standard analysis methods using the H$\beta$ index are found to produce spurious radially variable gradients.Comment: 15 pages, 9 figures, accepted by A

Variable Radio Sources in the Galactic Plane

Using three epochs of VLA observations of the Galactic Plane in the first quadrant taken ~15 years apart, we have conducted a search for a population of variable Galactic radio emitters in the flux density range 1-100 mJy at 6 cm. We find 39 variable sources in a total survey area of 23.2 sq deg. Correcting for various selection effects and for the extragalactic variable population of active galactic nuclei, we conclude there are ~1.6 Galactic sources per sq deg which vary by more than 50% on a time scale of years (or shorter). We show that these sources are much more highly variable than extragalactic objects; more than 50% show variability by a factor >2 compared to <10% for extragalactic objects in the same flux density range. We also show that the fraction of variable sources increases toward the Galactic center (another indication that this is a Galactic population), and that the spectral indices of many of these sources are flat or inverted. A small number of the variables are coincident with mid-IR sources and two are coincident with X-ray emitters, but most have no known counterparts at other wavelengths. Intriguingly, one lies at the center of a supernova remnant, while another appears to be a very compact planetary nebula; several are likely to represent activity associated with star formation regions. We discuss the possible source classes which could contribute to the variable cohort and followup observations which could clarify the nature of these sources.Comment: 11 pages, 7 figures; to be published in the Astronomical Journal; data available on MAGPIS website at http://third.ucllnl.org/gps

Analysis of substrate specificity of cytochrome P450 monooxygenases involved in trichothecene toxin biosynthesis

[EN]Trichothecenes are a structurally diverse family of toxic secondary metabolites produced by certain species of multiple fungal genera. All trichothecene analogs share a core 12,13-epoxytrichothec-9-ene (EPT) structure but differ in presence, absence and types of substituents attached to various positions of EPT. Formation of some of the structural diversity begins early in the biosynthetic pathway such that some producing species have few trichothecene biosynthetic intermediates in common. Cytochrome P450 monooxygenases (P450s) play critical roles in formation of trichothecene structural diversity. Within some species, relaxed substrate specificities of P450s allow individual orthologs of the enzymes to modify multiple trichothecene biosynthetic intermediates. It is not clear, however, whether the relaxed specificity extends to biosynthetic intermediates that are not produced by the species in which the orthologs originate. To address this knowledge gap, we used a mutant complementation-heterologous expression analysis to assess whether orthologs of three trichothecene biosynthetic P450s (TRI11, TRI13 and TRI22) from Fusarium sporotrichioides, Trichoderma arundinaceum, and Paramyrothecium roridum can modify trichothecene biosynthetic intermediates that they do not encounter in the organism in which they originated. The results indicate that TRI13 and TRI22 could not modify the intermediates that they do not normally encounter, whereas TRI11 could modify an intermediate that it does not normally encounter. These findings indicate that substrate promiscuity varies among trichothecene biosynthetic P450s. One structural feature that likely impacts the ability of the P450s to use biosynthetic intermediates as substrates is the presence and absence of an oxygen atom attached to carbon atom 3 of EPT.SIOpen Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature.Publicación en abierto financiada por el Consorcio de Bibliotecas Universitarias de Castilla y León (BUCLE), con cargo al Programa Operativo 2014ES16RFOP009 FEDER 2014-2020 DE CASTILLA Y LEÓN, Actuación:20007-CL - Apoyo Consorcio BUCL

A Deep Space Network Portable Radio Science Receiver

The Radio Science Receiver (RSR) is an open-loop receiver installed in NASA s Deep Space Network (DSN), which digitally filters and records intermediate-frequency (IF) analog signals. The RSR is an important tool for the Cassini Project, which uses it to measure perturbations of the radio-frequency wave as it travels between the spacecraft and the ground stations, allowing highly detailed study of the composition of the rings, atmosphere, and surface of Saturn and its satellites

Identification of polyketide synthase genes required for aspinolide biosynthesis in Trichoderma arundinaceum

https://link.springer.com/article/10.1007/s00253-022-12182-9[EN] The fungus Trichoderma arundinaceum exhibits biological control activity against crop diseases caused by other fungi. Two mechanisms that likely contribute to this activity are upregulation of plant defenses and production of two types of antifungal secondary metabolites: the sesquiterpenoid harzianum A (HA) and the polyketide-derived aspinolides. The goal of the current study was to identify aspinolide biosynthetic genes as part of an effort to understand how these metabolites contribute to the biological control activity of T. arundinaceum. Comparative genomics identified two polyketide synthase genes (asp1 and asp2) that occur in T. arundinaceum and Aspergillus ochraceus, which also produces aspinolides. Gene deletion and biochemical analyses in T. arundinaceum indicated that both genes are required for aspinolide production: asp2 for formation of a 10-member lactone ring and asp1 for formation of a butenoyl subsituent at position 8 of the lactone ring. Gene expression and comparative genomics analyses indicated that asp1 and asp2 are located within a gene cluster that occurs in both T. arundinaceum and A. ochraceus. A survey of genome sequences representing 35 phylogenetically diverse Trichoderma species revealed that intact homologs of the cluster occurred in only two other species, which also produced aspinolides. An asp2 mutant inhibited fungal growth more than the wild type, but an asp1 mutant did not, and the greater inhibition by the asp2 mutant coincided with increased HA production. These findings indicate that asp1 and asp2 are aspinolide biosynthetic genes and that loss of either aspinolide or HA production in T. arundinaceum can be accompanied by increased production of the other metabolite(s).SIPublicación en abierto financiada por el Consorcio de Bibliotecas Universitarias de Castilla y León (BUCLE), con cargo al Programa Operativo 2014ES16RFOP009 FEDER 2014-2020 DE CASTILLA Y LEÓN, Actuación:20007-CL - Apoyo Consorcio BUCL

The 6dF galaxy survey: Fundamental Plane data

We report the 6dFGS Fundamental Plane (6dFGSv) catalogue that is used to estimate distances and peculiar velocities for nearly 9000 early-type galaxies in the local (z < 0.055) universe. Velocity dispersions are derived by cross-correlation from 6dF V