Hydroxyl radical formation in the gas phase oxidation of distonic 2-methylphenyl radical cations

The reactions of distonic 4-(N, N, N-trimethylammonium)-2-methylphenyl and 5-(N, N, N-trimethylammonium)-2-methylphenyl radical cations (m/z 149) with O-2 are studied in the gas phase using ion-trap mass spectrometry. Photodissociation (PD) of halogenated precursors gives rise to the target distonic charge-tagged methylphenyl radical whereas collision-induced dissociation (CID) is found to produce unreactive radical ions. The PD generated distonic radicals, however, react rapidly with O-2 to form \[M + O2](center dot+) and \[M + O-2 - OH](center dot+) ions, detected at m/z 181 and m/z 164, respectively. Quantum chemical calculations using G3SX(MP3) and M06-2X theories are deployed to examine key decomposition pathways of the 5-(N, N, N-trimethylammonium)-2-methylphenylperoxyl radical and rationalise the observed product ions. The prevailing product mechanism involves a 1,5- H shift in the peroxyl radical forming a QOOH-type intermediate that subsequently eliminates (OH)-O-center dot to yield charge-tagged 2-quinone methide. Our study suggests that the analogous process should occur for the neutral methylphenyl + O-2 reaction, thus serving as a plausible source of (OH)-O-center dot radicals in combustion environments. Grants: ARC/DP0986738, ARC/DP130100862

Bisresorcinols and arbutin derivatives from Grevillea banksii R. Br

This work is part of a series of chemical investigations of the genus Grevillea. Two new arbutin derivatives, seven new bisresorcinols, including a mixture of two isomers, three known flavonol glycosides, and four known resorcinols, including a mixture of two homologous compounds, were isolated from the ethyl acetate extract of the leaves and methanol extract of the stems of Grevillea banksii. The new compounds were identified, on the basis of spectroscopic data, as 6'-O-(3-(2(hydroxymethyl)acryloyloxy)-2-methylpropanoyl)arbutin (1), 6'-O-(2-methylacryloyl)arbutin (2), 5,5'-(4(Z)-dodecen-1,12diyl)bisresorcinol (6), 2'-methyl-5,5'-(4(Z)-tetradecen-1,14-diyl)bisresorcinol (8), 2,2'-di(4-hydroxyprenyl)-5,5'-(6(Z)-tetradecen-1,14-diyl)bisresorcinol (9), 2-(4-acetoxyprenyl)-2'-(4-hydroxyprenyl) 5,5'-(6(Z)-tetradecen-1,14-diyl)bisresorcinol (10), 2-(4-acetoxyprenyl)-2'-(4-hydroxyprenyl)5,5'-(8(Z)-tetradecen-l,14-diyl)bisresorcinol (11), 5,5'-(10(Z)-tetradecen-1-on-diyl)bisresorcinol (12) and 5,5'-(4(Z)-tetradecen-1-on-diyl)bisresorcinol (13).

Formation of the heterocumulene anion SCCCN- by a cyano migration from the radical anion of 1,2-dicyanoethylenedithiolate

The anionic heterocumulene SCCCN- was generated in the gas phase by collisional activation of the radical anion of 1,2-dicyanoethylenedithiolate. The mechanism of this reaction, as well as the structures of neutral and anionic products, was investigated by hybrid density functional theory (DFT) calculations. Dissociation to form SCCCN- and SCN is proposed to occur by a radical directed cyano migration reaction, with calculations suggesting this is the lowest energy fragmentation pathway available to the precursor anion. In contrast, the even-electron protonated 1,2-dicyanoethylenedithiolate anion fragmented by loss of HCN.

Tethering for Selective Synthesis of 2,2′-Biphenols : the Acetal Method

2,2'-Biphenols are a large and diverse group of compounds with exceptional properties both as ligands and bioactive agents. Traditional methods for their synthesis by oxidative dimerisation are often problematic and lead to mixtures of ortho- and para-connected regioisomers. To compound these issues, an intermolecular dimerisation strategy is often inappropriate for the synthesis of heterodimers. The ‘acetal method’ provides a solution for these problems: stepwise tethering of two monomeric phenols enables heterodimer synthesis, enforces ortho regioselectivity and allows relatively facile and selective intramolecular reactions to take place. The resulting dibenzo[1,3]dioxepines have been analysed by quantum chemical calculations to obtain information about the activation barrier for ring flip between the enantiomers. Hydrolytic removal of the dioxepine acetal unit revealed the 2,2′-biphenol target.

Poly(2-oxazoline) hydrogels as next generation three dimensional cell supports

Synthetic hydrogels selectively decorated with cell adhesion motifs are rapidly emerging as promising substrates for 3D cell culture. When cells are grown in 3D they experience potentially more physiologically relevant cell-cell interactions and physical cues compared with traditional 2D cell culture on stiff surfaces. A newly developed polymer based on poly(2-oxazoline)s has been used for the first time to control attachment of fibroblast cells and is discussed here for its potential use in 3D cell culture with particular focus on cancer cells towards the ultimate aim of high throughput screening of anti-cancer therapies. Advantages and limitations of using poly(2-oxazoline) hydrogels are discussed and compared with more established polymers, especially polyethylene glycol (PEG).

The effectiveness of an intervention in reducing risk of dioxin exposure in Da Nang : changes in community knowledge, attitudes and prevention practices after 2.5 years

Introduction Environmental and biological samples taken around Da Nang Air Base have shown elevated levels of dioxin over many years [1-3]. A pre-intervention knowledge, attitudes and practices (KAP) survey (2009), a risk reduction program (2010) and a post intervention KAP survey (2011) were undertaken in four wards surrounding Danang Airbase. A follow-up evaluation was undertaken in 2013. Methods A KAP survey was implemented among 400 randomly selected food handlers. Eleven indepth interviews and four focus group discussions were also undertaken. Results The knowledge of respondents remained positive and/or improved at 2.5 years follow-up. There were no significant differences in attitudes toward preventing dioxin exposure across surveys; most respondents were positive in all three surveys. An increase in households (69.5%) undertaking measures to prevent exposure was observed, which was higher than in the pre-intervention survey (39.6%) and post- intervention survey (60.4%) (χ2 = 95.6; p < 0.001). The proportion of respondents practicing appropriate preventive measures was also significantly improved. Conclusions Despite most of the intervention program’s activities ceasing in 2010, the risk reduction program has resulted in positive outcomes over the longer-term, with many knowledge and attitude measures remaining stable or imporving. Some KAP indicators decreased, but these KAP indicators were still significantly higher than the pre-intervention levels.

The Black-tailed Antechinus, Antechinus arktos sp. nov.: a new species of carnivorous marsupial from montane regions of the Tweed Volcano caldera, eastern Australia

We describe a new species of dasyurid marsupial within the genus Antechinus that was previously known as a northern outlier of Dusky Antechinus (A. swainsonii). The Black-tailed Antechinus, Antechinus arktos sp. nov., is known only from areas of high altitude and high rainfall on the Tweed Volcano caldera of far south-east Queensland and north-east New South Wales, Australia. Antechinus arktos formerly sheltered under the taxonomic umbrella of A. swainsonii mimetes, the widespread mainland form of Dusky Antechinus. With the benefit of genetic hindsight, some striking morphological differences are herein resolved: A. s. mimetes is more uniformly deep brown-black to grizzled grey-brown from head to rump, with brownish (clove brown—raw umber) hair on the upper surface of the hindfoot and tail, whereas A. arktos is more vibrantly coloured, with a marked change from greyish-brown head to orange-brown rump, fuscous black on the upper surface of the hindfoot and dense, short fur on the evenly black tail. Further, A. arktos has marked orange-brown fur on the upper and lower eyelid, cheek and in front of the ear and very long guard hairs all over the body; these characters are more subtle in A. s. mimetes. There are striking genetic differences between the two species: at mtDNA, A. s. mimetes from north-east New South Wales is 10% divergent to A. arktos from its type locality at Springbrook NP, Queensland. In contrast, the Ebor A. s. mimetes clades closely with conspecifics from ACT and Victoria. A. arktos skulls are strikingly different to all subspecies of A. swainsonii. A. arktos are markedly larger than A. s. mimetes and A. s. swainsonii (Tasmania) for a range of craniodental measures. Antechinus arktos were historically found at a few proximate mountainous sites in south-east Queensland, and have only recently been recorded from or near the type locality. Even there, the species is likely in low abundance. The Black-tailed Antechinus has plausibly been detrimentally affected by climate change in recent decades, and will be at further risk with increasing warming trends.

ortho-Bromo(propa-1,2-dien-1-yl)arenes : substrates for domino reactions

o-Bromo(propa-1,2-dien-1-yl)arenes exhibit novel and orthogonal reactivity under Pd catalysis in the presence of secondary amines to form enamines (concerted Pd insertion, intramolecular carbopalladation, and terminative Buchwald–Hartwig coupling) and of amides to form indoles (addition, Buchwald–Hartwig cyclization, and loss of the acetyl group). The substrates for these reactions can be accessed in a reliable and highly selective two-step process from 2-bromoaryl bromides.