Talarolide A, a Cyclic Heptapeptide Hydroxamate from an Australian Marine Tunicate-Associated Fungus, <i>Talaromyces</i> sp. (CMB-TU011)

A miniaturized 24-well plate microbioreactor approach was used to explore secondary metabolite media dependence in an Australian marine tunicate-associated fungus, <i>Talaromyces</i> sp. (CMB TU011). Detailed chemical investigations of an antifungal M1-saline cultivation yielded talarolide A (<b>1</b>), only the second reported natural cyclic peptide hydroxamate, and the first from a fungus. The antifungal properties of the M1-saline extract were attributed to the known diterpene glycoside sordarin (<b>2</b>). Structure elucidation of <b>1</b> and <b>2</b> was achieved by detailed spectroscopic analysis, with amino acid configurations in <b>1</b> assigned by the C₃ and C₁₈ Marfey’s methods, and l-Ala and d-Ala regiochemistry by the recently reported 2D C₃ Marfey’s method

Trichodermides A–E: New Peptaibols Isolated from the Australian Termite Nest-Derived Fungus <i>Trichoderma virens</i> CMB-TN16

Chemical analysis of a fermentation of the Australian termite nest-derived fungus <i>Trichoderma virens</i> CMB-TN16 yielded five new acyclic nonapeptides, trichodermides A–E (<b>1</b>–<b>5</b>). Amino acid residues, configurations, and sequences were determined by a combination of spectroscopic (NMR and MS-MS) and chemical (C₃ Marfey’s) methods. The trichodermides adhere to the sequence homology pattern common to <i>Trichoderma</i> 11 amino acid residue peptaibols; however, unlike other peptaibols the trichodermides do not exhibit antibacterial or antifungal activity and exhibit low to no cytotoxicity against mammalian cells. This variability in biological activity highlights the importance of knowing both planar structures and absolute configurations when interpreting structure–activity relationships

Spongian-16-one Diterpenes and Their Anatomical Distribution in the Australian Nudibranch <i>Goniobranchus collingwoodi</i>

Six new (<b>1</b>–<b>6</b>) spongian-16-one analogues have been characterized from the Australian nudibranch species <i>Goniobranchus collingwoodi</i>, along with four known spongian-16-one derivatives. The structures and relative configuration were suggested by spectroscopic analyses informed by molecular modeling. Dissection of animal tissue revealed that the mantle and viscera differ in their terpene composition. Whole body extracts were not toxic to brine shrimp (<i>Artemia</i> sp.), but were unpalatable to palaemon shrimp (<i>Palaemon serenus</i>) at a concentration found within the nudibranch. Individual terpenes were not cytotoxic to human lung (NCIH-460), colorectal (SW620), and liver (HepG2) cancer cells

New PFASs Identified in AFFF Impacted Groundwater by Passive Sampling and Nontarget Analysis

Monitoring contamination from per- and polyfluoroalkyl substances (PFASs) in water systems impacted by aqueous film-forming foams (AFFFs) typically addresses a few known PFAS groups. Given the diversity of PFASs present in AFFFs, current analytical approaches do not comprehensively address the range of PFASs present in these systems. A suspect-screening and nontarget analysis (NTA) approach was developed and applied to identify novel PFASs in groundwater samples contaminated from historic AFFF use. A total of 88 PFASs were identified in both passive samplers and grab samples, and these were dominated by sulfonate derivatives and sulfonamide-derived precursors. Several ultrashort-chain (USC) PFASs (≤C3) were detected, 11 reported for the first time in Australian groundwater. Several transformation products were identified, including perfluoroalkane sulfonamides (FASAs) and perfluoroalkane sulfinates (PFASis). Two new PFASs were reported (((perfluorohexyl)sulfonyl)sulfamic acid; m/z 477.9068 and (E)-1,1,2,2,3,3,4,5,6,7,8,8,8-tridecafluorooct-6-ene-1-sulfonic acid; m/z 424.9482). This study highlights that several PFASs are overlooked using standard target analysis, and therefore, the potential risk from all PFASs present is likely to be underestimated