Michael Gallen

Total synthesis of (+)-5, 14-bis-epi-Spirovibsanin A

The total synthesis of (+/-)-5,14-bis-epi-spirovibsanin A was achieved in 18 steps. Physical data obtained from (+/-)-5,14-bis-epi-spirovibsanin A lends strong support to the proposed connectivity and relative stereochemistry of spirovibsanin A.

Occurrence and distribution of brominated flame retardants and perfluoroalkyl substances in Australian landfill leachate and biosolids

The levels of perfluroalkyl substances (PFASs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDDs) were studied in Australian landfill leachate and biosolids. Leachate was collected from 13 landfill sites and biosolids were collected from 16 wastewater treatment plants (WWTPs), across Australia. Perfluorohexanoate (PFHxA) (12-5700ng/L) was the most abundant investigated persistent, bioaccumulative and toxic (PBT) chemical in leachate. With one exception, mean concentrations of PFASs were higher in leachate of operating landfills compared to closed landfills. Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane isomers (HBCDDs) were detected typically at operating landfills in comparatively lower concentrations than the PFASs. Decabromodiphenyl ether (BDE-209) (<0.4-2300ng/g) and perfluoroctanesulfonate (PFOS) (<LOD-380ng/g) were the predominant PBTs detected in biosolids. Using data provided by sites, the volume of leachate discharged to WWTPs for treatment was small (<1% total inflow), and masses of PBTs transferred reached a maximum of 16g/yr (PFHxA). A national estimate of masses of PBTs accumulated in Australian biosolids reached 167kg/yr (BDE-209), a per capita contribution of 7.2±7.2mg/yr. Nationally, approximately 59% of biosolids are repurposed and applied to agricultural land. To our knowledge this study presents the first published data of PFASs and HBCDDs in Australian leachate and biosolids.

Emissions of Selected Semivolatile Organic Chemicals from Forest and Savannah Fires

The emission factors (EFs) for a broad range of semivolatile organic chemicals (SVOCs) from subtropical eucalypt forest and tropical savannah fires were determined for the first time from in situ investigations. Significantly higher (t test, P < 0.01) EFs (μg kg-1 dry fuel, gas + particle-associated) for polycyclic aromatic hydrocarbons (∑13 PAHs) were determined from the subtropical forest fire (7,000 ± 170) compared to the tropical savannah fires (1,600 ± 110), due to the approximately 60-fold higher EFs for 3-ring PAHs from the former. EF data for many PAHs from the eucalypt forest fire were comparable with those previously reported from pine and fir forest combustion events. EFs for other SVOCs including polychlorinated biphenyl (PCB), polychlorinated naphthalene (PCN), and polybrominated diphenyl ether (PBDE) congeners as well as some pesticides (e.g., permethrin) were determined from the subtropical eucalypt forest fire. The highest concentrations of total suspended particles, PAHs, PCBs, PCNs, and PBDEs, were typically observed in the flaming phase of combustion. However, concentrations of levoglucosan and some pesticides such as permethrin peaked during the smoldering phase. Along a transect (10-150-350 m) from the forest fire, concentration decrease for PCBs during flaming was faster compared to PAHs, while levoglucosan concentrations increased.

[4+2] Cycloaddition Reactions Between 1,8‐Disubstituted Cyclooctatetraenes and Diazo Dienophiles: Stereoelectronic Effects, Anticancer Properties and Application to the Synthesis of 7,8‐Substituted Bicyclo[4.2.0]octa‐2,4‐dienes

A detailed examination of [4+2] cycloaddition reactions between 1,8-disubstituted cyclooctatetraenes and diazo compounds revealed that 4-phenyl-1,2,4-triazole-3,5-dione (PTAD) reacts to form either 2,3- or 3,4-disubstituted adducts. The product distribution can be controlled by modulating the electron density of the cyclooctatetraene. Unprecedented [4+2] cycloadditions between diisopropyl azodicarboxylate (DIAD) and 1,8-disubstituted cyclooctatetraenes are also described and further manipulation of a resulting cycloadduct uncovered a new pathway to the synthetically challenging bicyclo[4.2.0]octa-2,4-diene family. Variation of the substituents resulted in a range of compounds displaying selective action against different human tumour cell types.