Repurposing the Pummerer Rearrangement: Determination of Methionine Sulfoxides in Peptides

The reversible oxidation of methionine residues in proteins has emerged as a biologically important post-translational modification. However, detection and quantitation of methionine sulfoxide in proteins is difficult. Our aim is to develop a method for specifically derivatizing methionine sulfoxide residues. We report a Pummerer rearrangement of methionine sulfoxide treated sequentially with trimethylsilyl chloride and then 2-mercaptoimidazole or pyridine-2-thiol to produce a dithioacetal product. This derivative is stable to standard mass spectrometry conditions, and its formation identified oxidized methionine residues. The scope and requirements of dithioacetal formation are reported for methionine sulfoxide and model substrates. The reaction intermediates have been investigated by computational techniques and by ¹³C NMR spectroscopy. These provide evidence for an α-chlorinated intermediate. The derivatization allows for detection and quantitation of methionine sulfoxide in proteins by mass spectrometry and potentially by immunochemical methods.     

Supporting perspective taking across chasms of thinking: Do real-time analytics hold the key?

International Journal of Computer-Supported Collaborative Learning -     

Risk Perceptions and Terror Management Theory: Assessing Public Responses to Urban Flooding in Toronto,Canada

Terror Management Theory (TMT) suggests that mortality salience (MS), or death reminders, should impact environmental behaviour and decision-making by increasing consumption and resource usage, shifting aesthetic preferences toward cultivated landscapes, and affecting adherence to environmental norms. We examined MS effects on residential flood risk perceptions in Toronto, Canada, following the major urban flood in July 2013. Survey responses were analyzed to assess risk perceptions across nine categories; analyses through the Wilcoxon-Mann–Whitney test show statistically insignificant differences between MS and control groups for all subcategories. Coupled with the TMT literature, the results indicate that existential anxiety is more likely to affect flood risk perceptions through worldview defense when the social dimension of flooding is made clear. Toronto residents’ societal beliefs about flooding play a major role in guiding flood management strategies. Our results provide scholarly and practical direction for flood risk communication strategies to promote the adoption of private flood-prevention measures, suggesting that anthropocentric framing of flooding issues will not induce negative environmental behaviour and may increase concern for flooding issues.     

Partnerships for disability-inclusive road development in Papua New Guinea: Unusual suspects and equivocal gains

This article examines how an action research partnership developed and then influenced social justice outcomes during a 3-year research project to promote disability-inclusive road development in Papua New Guinea. The purpose of this article is to reflect on possible reasons why this partnership obtained certain positive results and not others. By reflecting on how the partnership developed, transformed over time, engendered achievements and failures, and affected the individuals and organizations involved in it, I aim to contribute to the understanding of how collaborative research partnerships can better promote the rights of those who are often marginalized from public space and decision-making. In this case study, neo-colonialism and underlying tensions between engineering and social development “world views”, both within and between partners, affected both positive outcomes and lost opportunities in terms of improving the lives of people with disabilities.     

Poly(methyl methacrylate)‐grafted cellulose nanocrystals: One‐step synthesis,nanocomposite preparation,and characterization

Cellulose nanocrystals (CNCs) are ideal reinforcing agents for polymer nanocomposites because they are lightweight and nano‐sized with a large aspect ratio and high elastic modulus. To overcome the poor compatibility of hydrophilic CNCs in non‐polar composite matrices, we grafted poly(methyl methacrylate) (PMMA) from the surface of CNCs using an aqueous, one‐pot, free radical polymerization method with ceric ammonium nitrate as the initiator. The hybrid nanoparticles were characterized by CP/MAS NMR, X‐ray photoelectron spectroscopy, infrared spectroscopy, contact angle, thermogravimetric analysis, X‐ray diffraction, and atomic force microscopy. Spectroscopy demonstrates that 0.11 g/g (11 wt %) PMMA is grafted from the CNC surface, giving PMMA‐g‐CNCs, which are similar in size and crystallinity to unmodified CNCs but have an onset of thermal degradation 45 °C lower. Nanocomposites were prepared by compounding unmodified CNCs and PMMA‐g‐CNCs (0.0025–0.02 g/g (0.25–2 wt %) loading) with PMMA using melt mixing and wet ball milling. CNCs improved the performance of melt‐mixed nanocomposites at 0.02 g/g (2 wt %) loading compared to the PMMA control, while lower loadings of CNCs and all loadings of PMMA‐g‐CNCs did not. The difference in Young's modulus between unmodified CNC and polymer‐grafted CNC composites was generally insignificant. Overall, ball‐milled composites had inferior mechanical and rheological properties compared to melt‐mixed composites. Scanning electron microscopy showed aggregation in the samples with CNCs, but more pronounced aggregation with PMMA‐g‐CNCs. Despite improving interfacial compatibility between the nanoparticles and the matrix, the effect of PMMA‐g‐CNC aggregation and decreased thermal stability dominated the composite performance.     

Polyphenol conjugated poly(beta-amino ester) polymers with hydrogen peroxide triggered degradation and active antioxidant release

Oxidative stress has been implicated as a primary or secondary player to numerous diseases. A potential approach to control oxidative stress induced diseases is to deliver small antioxidant compounds to compromised sites at equivalent rates of reactive oxygen species (ROS) generation. This becomes a complicated task as antioxidant molecules typically have poor bioavailability and stability. Antioxidants synthesized into poly(beta-amino ester) (PBAE) crosslinked polymers have shown improved delivery by enhancing stability while allowing controlled release through hydrolysis. The tunable crosslinked networks show significant response to specific oxidizing environments, where free radicals can be present. Curcumin conjugated PBAE bulk films have proportional rates of accelerated degradation, thus faster release of curcumin, in a range of low concentrations of hydrogen peroxide (H₂O₂)_, where 2′2-azobis(2-amidinopropane) dihydrochloride has no substantial impact. This effect suggests the possibility to create a system that releases its therapeutic agent in direct relationship to the need through ROS signaling. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48647.     

Salmonella in uncooked retail meats in New Zealand

A national quantitative survey of Salmonella in five types of uncooked retail meats in New Zealand was undertaken from August 2003 to May 2005 to establish baseline proportionality data. The overall prevalence of Salmonella in 1,108 meat samples was 1.1% (95% confidence interval, 0.6 to 1.9). Low prevalences of Salmonella in each meat type were observed, with 3% (1.2 to 6.1) in chicken, 1.3% (0.3 to 3.8) in lamb and mutton, 0.5% (0 to 3.0) in unweaned veal, 0.4% (0 to 2.4) in beef, and 0% (0 to 1.6) in pork. The Salmonella serotypes isolated were Salmonella Infantis from beef; Salmonella Typhimurium PT1 from unweaned veal and chicken; Salmonella sp. 6,7:k:-, Salmonella Enteritidis PT9a, Salmonella sp. 4,5,12:-:-, Salmonella sp. 4,12:-:-, and Salmonella Typhimurium PT160 from chicken; and Salmonella sp. 4:-:2 and Salmonella Brandenburg from lamb. Four of the isolates from chicken, Salmonella sp. 4,5,12:-:- (two isolates), Salmonella sp. 4,12:-:-, and Salmonella Typhimurium PT1, were very similar phenotypically and serologically to the attenuated Salmonella vaccine strain used in MeganVacl for poultry. One lamb sample yielded a count of Salmonella Brandenburg of 4.24 most probable number (MPN)/g, while all other positive samples were <1.0 MPN/g. The results provide baseline proportionality data for Salmonella in retail uncooked meats that will contribute invaluably toward future risk assessment in light of other information, such as consumption data that can be used for risk characterization.     

Authenticity Assessment of Extra Virgin Olive Oil: Evaluation of Desmethylsterols and Triterpene Dialcohols

Extra virgin olive oil (EVOO) has a long history of economic adulteration, the detection of which presents significant challenges due to the diverse composition of cultivars grown around the world and the limitations of existing methods for detecting adulteration. In this study, using Method COI/T.20/Doc. No. 30/Rev. 1 of the International Olive Council, the authenticity of 88 market samples of EVOO was evaluated by comparing total sterol contents, desmethylsterol composition, and contents of triterpene dialcohols (erythrodiol and uvaol) with purity criteria specified in the United States Standards for grades of olive oil and olive‐pomace oil. Three of the 88 samples labeled as EVOO failed to meet purity criteria, indicating possible adulteration with commodity oil and/or solvent‐extracted olive oil. Detection of adulteration was also evaluated by spiking an EVOO sample with commodity oil at the 10 % level. As expected, eight of the spiked samples (canola, corn, hazelnut, peanut, safflower, soybean, and sunflower oils, and palm olein) failed to meet purity criteria. Two of the three samples spiked with 10 % hazelnut oil went undetected for adulteration. Overall, a low occurrence rate of adulteration (<5 %), based on purity criteria for desmethylsterols and triterpene dialcohols, was detected for the 88 products labeled as EVOO.     

Olfactory responses ofIps plastographus maritimus lanier (coleoptera: Scolytidae) to insect and host-associated volatiles in the laboratory

Attraction of both sexes ofIps plastographus maritimus Lanier to bark-phloem-xylem discs of Monterey pine,Pinus radiata D. Don, was demonstrated in the laboratory. Increasing concentrations of male and female volatiles trapped separately and released in a one-to-one ratio decreased attraction for both sexes combined. Attraction of both sexes to volatiles derived from males and females tunneling together in a one-to-one ratio increased with increasing concentration of extract. Attraction of males and females to male-infested discs and to trapped male volatiles increased with increasing dose of males or male extract. Attraction of males and females to female-infested discs and to trapped female volatiles was also demonstrated. The presence of females in male galleries reduced the attractiveness of infested disks to both sexes combined. Increasing numbers of females, tunneling separately from males in the same disc, reduced attraction of males, but not females. When a constant attractive dose of male volatiles was released with increasing doses of female volatiles, there was no difference in response of either sex when female volatiles were present compared with the response to male volatiles alone. When a constant attractive dose of male volatiles was released with increasing concentrations of volatiles derived from males and females tunneling together in a one-to-one ratio, attraction ofI. p. maritimus decreased. Response of females was frequently higher than that of males to the same attractant source. Hence, both sexes produce an attractant, and both sexes tunneling together in the same gallery reduce attraction of males and females to an attractive dose of male attractant.