BackgroundErgosterol has been considered the “fungal sterol” for almost 125 years; however, additional sterol data superimposed on a recent molecular phylogeny of kingdom Fungi reveals a different and more complex situation.Methodology/Principal FindingsThe interpretation of sterol distribution data in a modern phylogenetic context indicates that there is a clear trend from cholesterol and other Δ5 sterols in the earliest diverging fungal species to ergosterol in later diverging fungi. There are, however, deviations from this pattern in certain clades. Sterols of the diverse zoosporic and zygosporic forms exhibit structural diversity with cholesterol and 24-ethyl -Δ5 sterols in zoosporic taxa, and 24-methyl sterols in zygosporic fungi. For example, each of the three monophyletic lineages of zygosporic fungi has distinctive major sterols, ergosterol in Mucorales, 22-dihydroergosterol in Dimargaritales, Harpellales, and Kickxellales (DHK clade), and 24-methyl cholesterol in Entomophthorales. Other departures from ergosterol as the dominant sterol include: 24-ethyl cholesterol in Glomeromycota, 24-ethyl cholest-7-enol and 24-ethyl-cholesta-7,24(28)-dienol in rust fungi, brassicasterol in Taphrinales and hypogeous pezizalean species, and cholesterol in Pneumocystis.Conclusions/SignificanceFive dominant end products of sterol biosynthesis (cholesterol, ergosterol, 24-methyl cholesterol, 24-ethyl cholesterol, brassicasterol), and intermediates in the formation of 24-ethyl cholesterol, are major sterols in 175 species of Fungi. Although most fungi in the most speciose clades have ergosterol as a major sterol, sterols are more varied than currently understood, and their distribution supports certain clades of Fungi in current fungal phylogenies. In addition to the intellectual importance of understanding evolution of sterol synthesis in fungi, there is practical importance because certain antifungal drugs (e.g., azoles) target reactions in the synthesis of ergosterol. These findings also invalidate use of ergosterol as an indicator of biomass of certain fungal taxa (e.g., Glomeromycota). Data from this study are available from the Assembling the Fungal Tree of Life (AFTOL) Structural and Biochemical Database: http://aftol.umn.edu.

No abstract

: Post-emergence application of carfentrazone-ethyl at rates as low as 2É2 g ha~1 caused greater leaf injury and growth reduction in ivyleaf morningglory (Ipomoea hederacea) and velvetleaf (Abutilon theophrasti) than in soybean (Glycine max). The herbicide was more rapidly metabolized in the crop than in the weed species, with 26É7, 54É3 and 60É6% of the parent compound remaining in soybean, ivyleaf morningglory and velvetleaf, respectively, 24 h after exposure. The free acid metabolite, carfentrazone, was present in all species and accounted for 21É2È27É4% of the total radioactivity. Unknown metabolites 0 and 0É22) were four to Ðve times more abundant in soybean than in the (R f weed species. Carfentrazone-ethyl induced more leakage from leaf discs from the weeds than those from soybean and the degree of injury correlated with the amount of protoporphyrin IX (Proto IX) present in the treated tissues. Both carfentrazone-ethyl and carfentrazone were potent inhibitors of protoporphyrinogen oxidase (Protox). Therefore, the selectivity of this herbicide may, at least in part, be attributed to the lower accumulation of Proto IX in soybean than in the weeds, probably because of the ability of soybean to metabolize more carfentrazone into unknown metabolites than the weeds.

No abstract

Consistent with field observations, sicklepod exhibited considerable tolerance to sulfentrazone, and coffee senna showed relatively high sensitivity to this herbicide in greenhouse tests. Germination was not inhibited in either species at up to 12.9 μM of the herbicide. However, the chlorophyll content of herbicide-treated coffee senna cotyledonary leaves was greatly reduced, and seedlings died within 10 d after treatment, while sicklepod seedlings were not visibly affected. Shoot height of coffee senna was inhibited 90% by sulfentrazone at 0.5 kg ai ha−1, while the growth of sicklepod was not affected up to 2.0 kg ai ha−1. Root uptake of radiolabeled sulfentrazone was 74% greater in coffee senna than sicklepod, but the amount of radioactivity recovered from the shoots of both species after 12 h was not different. Eighty-three percent of the parent compound remained in coffee senna leaf tissue after 9 h root exposure to the herbicide. In contrast, sicklepod took up relatively less sulfentrazone through the root and metabolized sulfentrazone in the foliage more rapidly than coffee senna, with 91.6% of the herbicide being metabolized during the first 9 h of exposure. These results suggest that the tolerance of sicklepod to sulfentrazone is primarily due to a relatively high rate of metabolism of the herbicide compared to coffee senna.

No abstract

Sulfentrazone was foliar applied at 34 and 56 g ai ha−1alone or in combination with surfactants to soybean cultivars Hutcheson and Centennial and to sicklepod, coffee senna, smallflower morningglory, velvetleaf, and yellow nutsedge. The most sensitive weeds, including coffee senna, smallflower morningglory, and velvetleaf, were severely injured by the lowest rate when sulfentrazone was applied with surfactants. Sulfentrazone provided the highest control of yellow nutsedge with X-77. Soybeans were not severely injured by sulfentrazone applied alone, but 55% foliar injury occurred when the herbicide was applied with X-77. However, the seedlings were not killed. Sicklepod was the most tolerant of the weeds tested. In the absence of surfactants, the order of radiolabeled sulfentrazone absorption by the foliage was Centennial (5.8%) = Hutcheson (8.5%) = coffee senna (10.4%) < yellow nutsedge (17.0%) < velvetleaf (22.3%) = smallflower morningglory (24%). Sicklepod leaves did not retain droplets containing sulfentrazone when no surfactant was used. Species with the highest foliar absorption also showed the greatest phytotoxic response to the herbicide. Addition of surfactants to the spray mixture enhanced the foliar absorption and overall phytotoxicity of sulfentrazone in the weeds. An inverse relationship was detected between the foliar absorption of sulfentrazone without surfactants and the amount of cuticular wax present on the leaves. No such correlation was observed when surfactants were used. Thus, surfactants overcame the barrier to absorption imposed by the cuticular wax and, under these conditions, selectivity apparently became dependent upon species-specific cellular tolerance to sulfentrazone.

Sulfentrazone persistence in soil requires many crop rotational restrictions. The sorption and mobility of sulfentrazone play an important role in its soil persistence. Thus, a series of laboratory experiments were conducted to mimic the soil properties of cation and anion exchange with different intermediates. The molecular characterization and ionization shift of sulfentrazone from a neutral molecule to an anion were determined using a three-dimensional graphing technique and titration curve, respectively. Sorption and mobility of 2.6 × 10−5 M 14C-sulfentrazone were evaluated using a soil solution technique with ion exchange resins and polyacrylamide gel electrophoresis, respectively. Solution pH ranged from 4.0 to 7.4. As pH increased, sulfentrazone sorption to an anion resin increased and its sorption to a cation resin decreased. Percent sulfentrazone in solution was pH-dependent and ranged between 0 to 18% and 54 to 88% for the anion and cation resins, respectively. Mobility of sulfentrazone on a 20% polyacryalmide gel resulted in Rf values of +0.02 and +0.39 for pH of 4.0 and 7.4, respectively. A double peak for sulfentrazone was detected in the polyacrylamide gel when the pH (6.0 and 6.8) was near the reported pKa of 6.56. There was no clear interaction for the sorption of sulfentrazone at 1.0 mg kg−1 to Congaree loamy sand or Decatur silty clay loam saturated with either calcium or potassium. Sulfentrazone behavior with the polyacrylamide electrophoresis gels and ion resins indicate the potential for this herbicide to occur as a polar or Zwitter ion. Sulfentrazone was adsorbed by potassium, calcium, and sodium saturated resins and subsequently desorbed using variable pH solutions. The level of sulfentrazone adsorption will vary among soil types and the amount of desorption into solution may be soil cation-dependent.