Response of real-time black carbon mass instruments to mini-CAST soot

Soot is a climate forcer and a dangerous air pollutant that has been increasingly regulated. In aviation, regulatory measurements of soot mass concentration in the exhaust of aircraft turbine engines are to be based on measurements of black carbon (BC) calibrated to elemental carbon (EC) content of diffusion flame soot. The calibration soot must currently meet only one criterion: minimum EC to total carbon (TC) ratio of 0.8. However, not including soot properties other than the EC/TC ratio may potentially lead to discrepancies between different BC measurements. We studied the response of two instruments, the AVL Micro-Soot Sensor (MSS) and the Artium Laser-Induced Incandescence 300 (LII), to soot from two miniature combustion aerosol standard (mini-CAST) burners. By changing the air-fuel ratio, premixing nitrogen into the fuel, and using a catalytic stripper to remove volatile compounds, we produced a wide range of particle morphologies and EC contents. As the EC content decreased, both the instruments underreported the EC mass, but the LII diverged more severely. Upon closer investigation of eight conditions with EC/TC > 0.8, the LII underreporting was found independent of primary particle size, but increased with decreasing geometric mean diameter of the soot agglomerates. As the geometric mean diameter decreased from 160 nm to 50 nm, the differences between the LII and MSS increased from 15% to 50%. The results suggest that in addition to EC content, calibration procedures for the regulatory BC measurements may need to take particle size distributions into account.

© 2016 American Association for Aerosol Research     

Development of Simplified Heterocyclic Acetogenin Analogues as Potent and Selective Trypanosoma brucei Inhibitors

Neglected tropical diseases caused by parasitic infections are an ongoing and increasing concern. They are a burden to human and animal health, having the most devastating effect on the world′s poorest countries. Building upon our previously reported triazole analogues, in this study we describe the synthesis and biological testing of other novel heterocyclic acetogenin‐inspired derivatives, namely 3,5‐isoxazoles, furoxans, and furazans. Several of these compounds maintain low‐micromolar levels of inhibition against Trypanosoma brucei, whilst having no observable inhibitory effect on mammalian cells, leading to the possibility of novel lead compounds for selective treatment.     

Ebola Entry Inhibitors Discovered from Maesa perlarius

Ebola virus disease (EVD), a disease caused by infection with Ebola virus (EBOV), is characterized by hemorrhagic fever and a high case fatality rate. With limited options for the treatment of EVD, anti-Ebola viral therapeutics need to be urgently developed. In this study, over 500 extracts of medicinal plants collected in the Lingnan region were tested against infection with Ebola-virus-pseudotyped particles (EBOVpp), leading to the discovery of Maesa perlarius as an anti-EBOV plant lead. The methanol extract (MPBE) of the stems of this plant showed an inhibitory effect against EBOVpp, with an IC₅₀ value of 0.52 µg/mL, which was confirmed by testing the extract against infectious EBOV in a biosafety level 4 laboratory. The bioassay-guided fractionation of MPBE resulted in three proanthocyanidins (procyanidin B2 (1), procyanidin C1 (2), and epicatechin-(4β→8)-epicatechin-(4β→8)-epicatechin-(4β→8)-epicatechin (3)), along with two flavan-3-ols ((+)-catechin (4) and (−)-epicatechin (5)). The IC₅₀ values of the compounds against pseudovirion-bearing EBOV-GP ranged from 0.83 to 36.0 µM, with 1 as the most potent inhibitor. The anti-EBOV activities of five synthetic derivatives together with six commercially available analogues, including EGCG ((−)-epigallocatechin-3-O-gallate (8)), were further investigated. Molecular docking analysis and binding affinity measurement suggested the EBOV glycoprotein could be a potential molecular target for 1 and its related compounds.     

Synthetic Activity of Recombinant Whole Cell Biocatalysts Containing 2-Deoxy-D-ribose-5-phosphate Aldolase from Pectobacterium atrosepticum

In nature 2-deoxy-D-ribose-5-phosphate aldolase (DERA) catalyses the reversible formation of 2-deoxyribose 5-phosphate from D-glyceraldehyde 3-phosphate and acetaldehyde. In addition, this enzyme can use acetaldehyde as the sole substrate, resulting in a tandem aldol reaction, yielding 2,4,6-trideoxy-D-erythro-hexapyranose, which spontaneously cyclizes. This reaction is very useful for the synthesis of the side chain of statin-type drugs used to decrease cholesterol levels in blood. One of the main challenges in the use of DERA in industrial processes, where high substrate loads are needed to achieve the desired productivity, is its inactivation by high acetaldehyde concentration. In this work, the utility of different variants of Pectobacterium atrosepticum DERA (PaDERA) as whole cell biocatalysts to synthesize 2-deoxyribose 5-phosphate and 2,4,6-trideoxy-D-erythro-hexapyranose was analysed. Under optimized conditions, E. coli BL21 (PaDERA C-His AA C49M) whole cells yields 99 % of both products. Furthermore, this enzyme is able to tolerate 500 mM acetaldehyde in a whole-cell experiment which makes it suitable for industrial applications.     

The effect of stoichiometry on the fracture toughness of a liquid crystalline epoxy

The fracture toughness of a liquid crystalline epoxy was compared with that of a standard bisphenol‐A based epoxy to understand how both the liquid crystalline structure and the crosslink density affect fracture toughness. For the liquid crystalline epoxy, the liquid crystalline domain size decreased with increasing temperature of cure and away from the stoichiometric formulation. Quantitative fractography showed that there is a competition between the liquid crystalline domain structure and the stoichiometry in determining the fracture toughness. At some cure conditions the effect of the domains is dominant. When the cure conditions are adjusted to reduce the domain size, the domains become too small to affect the fracture toughness, and thus the effect of the stoichiometry is dominant. The result is that the formation of liquid crystalline structure only increases the fracture toughness relative to that of a traditional epoxy at and near the stoichiometric formulation.     

Ab Initio Calculations of Pristine and Doped Zirconia Σ5 (310)/[001] Tilt Grain Boundaries

The structure of the cubic-ZrO₂ symmetrical tilt Σ5 (310)/[001] grain boundary is examined using density functional theory within the local density and pseudopotential approximations. Several pristine stoichiometric grain-boundary structures are investigated and compared with Z-contrast scanning transmission electron microscopy and electron energy loss spectroscopy results. The lowest-energy grain-boundary structure is found to agree well with the experimental data. When Y³⁺ is substituted for Zr⁴⁺ at various sites in the lowest-energy grain-boundary structure, the calculations indicate that Y³⁺ segregation to the grain boundary is energetically preferred to bulk doping, in agreement with experimental results.     

A Genetically-Based Latitudinal Cline in the Emission of Herbivore-Induced Plant Volatile Organic Compounds

The existence of predictable latitudinal variation in plant defense against herbivores remains controversial. A prevailing view holds that higher levels of plant defense evolve at low latitudes compared to high latitudes as an adaptive plant response to higher herbivore pressure on low-latitude plants. To date, this prediction has not been examined with respect to volatile organic compounds (VOCs) that many plants emit, often thus attracting the natural enemies of herbivores. Here, we compared genetically-based constitutive and herbivore-induced aboveground vegetative VOC emissions from plants originating across a gradient of more than 10° of latitude (>1,500 km). We collected headspace VOCs from Asclepias syriaca (common milkweed) originating from 20 populations across its natural range and grown in a common garden near the range center. Feeding by specialist Danaus plexippus (monarch) larvae induced VOCs, and field environmental conditions (temperature, light, and humidity) also influenced emissions. Monarch damage increased plant VOC concentrations and altered VOC blends. We found that genetically-based induced VOC emissions varied with the latitude of plant population origin, although the pattern followed the reverse of that predicted—induced VOC concentration increased with increasing latitude. This pattern appeared to be driven by a greater induction of sesquiterpenoids at higher latitudes. In contrast, constitutive VOC emission did not vary systematically with latitude, and the induction of green leafy volatiles declined with latitude. Our results do not support the prevailing view that plant defense is greater at lower than at higher latitudes. That the pattern holds only for herbivore-induced VOC emission, and not constitutive emission, suggests that latitudinal variation in VOCs is not a simple adaptive response to climatic factors.     

Improvement of Major Depression is Associated with Increased Erythrocyte DHA

The aim of this study was to determine if changes in omega‐3 polyunsaturated fatty acid status following tuna oil supplementation correlated with changes in scores of depression. A total of 95 volunteers receiving treatment for major depression were randomised to consume 8 × 1 g capsules per day of HiDHA (2 g DHA, 0.6 g EPA and 10 mg Vitamin E) or olive oil (placebo) for 16 weeks, whilst undergoing weekly counseling sessions by trained clinical psychologists using a standard empirically validated psychotherapy. Depression status was assessed using the 17 item Hamilton rating scale for depression and the Beck Depression Inventory by a psychodiagnostician who was blind to the treatment. Blood was taken at baseline and 16 weeks (n = 48) for measurement of erythrocyte fatty acids. With HiDHA supplementation, erythrocyte DHA content rose from 4.1 ± 0.2 to 7.9 ± 0.4 % (mean ± SEM, p < 0.001) of total fatty acids but did not change (4.0 ± 0.2 to 4.1 ± 0.2 %) in the olive oil group. The mean changes in scores of depression did not differ significantly between the two groups (?12.2 ± 2.1 for tuna oil and ?14.4 ± 2.3 for olive oil). However, analysis of covariance showed that in the fish oil group there was a significant correlation (r = ?0.51) between the change in erythrocyte DHA and the change in scores of depression (p < 0.05). Further study of the relationship between DHA and depression is warranted.     

The molecular structure of asphaltene: an unfolding story

From detailed chemical and thermal degradation studies, a host of structural units have been identified in Alberta asphaltenes. It has been shown that the extent of aromatic condensation is low and that highly condensed pericyclic aromatic structures are present in very low concentrations. From the available data reported to date, it is concluded that petroleum asphaltenes were mainly derived through the catalytic cyclization, aromatization and condensation of n-alkanoic, probably fatty acids, precursors.