Metal complexation properties of freshwater dissolved organic matter are explained by its aromaticity and by anthropogenic ligands

Dissolved organic matter (DOM) in surface waters affects the fate and environmental effects of trace metals. We measured variability in the Cd, Cu, Ni, and Zn affinity of 23 DOM samples isolated by reverse osmosis from freshwaters in natural, agricultural, and urban areas. Affinities at uniform pH and ionic composition were assayed at low, environmentally relevant free Cd, Cu, Ni, and Zn activities. The C-normalized metal binding of DOM varied 4-fold (Cu) or about 10-fold (Cd, Ni, Zn) among samples. The dissolved organic carbon concentration ranged only 9-fold in the waters, illustrating that DOM quality is an equally important parameter for metal complexation as DOM quantity. The UV-absorbance of DOM explained metal affinity only for waters receiving few urban inputs, indicating that in those waters, aromatic humic substances are the dominant metal chelators. Larger metal affinities were found for DOM from waters with urban inputs. Aminopolycarboxylate ligands (mainly EDTA) were detected at concentrations up to 0.14 μM and partly explained the larger metal affinity. Nickel concentrations in these surface waters are strongly related to EDTA concentrations (R2=0.96) and this is underpinned by speciation calculations. It is concluded that metal complexation in waters with anthropogenic discharges is larger than that estimated with models that only take into account binding on humic substances.     

Effects of fluid–fluid interfacial elasticity on droplet formation in microfluidic devices

Biomolecules adsorb at fluid–fluid interfaces and can form a cohesive interfacial network imparting distinctive local interfacial mechanics. This modification of interfacial behavior is empirically known to significantly affect the stability and flow behavior of foams and emulsions. Droplet formation in the presence of interfacial networks is investigated in a flow‐focusing microfluidic device using designed peptide surfactants, which allow decoupled control of interfacial rheology and interfacial tension. The influence of interfacial elasticity on droplet breakup, satellite droplet formation and droplet size are reported. The presence of high interfacial elasticity strongly affects the mechanism of droplet breakup by delaying neck thinning and altering interfacial shape at the point of droplet detachment, resulting in the suppression of satellite droplet formation and a decrease in droplet size. We report a correlation between dimensionless droplet size and a new dimensionless grouping which combines flow‐rate ratio with the ratio of interfacial tension and interfacial elasticity. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Purification,Stereoisomeric Analysis and Quantification of Sex Pheromone Precursors in Female Whole Body Extracts from Pine Sawfly Species

A GC-MS method to analyze the stereoisomeric composition of chiral secondary alcohols found in whole body extracts of pine sawfly females was developed. The tested alcohols were derivatized with optically pure (S)-2-acetoxypropionyl chloride prior to GC-MS analysis. Baseline separation was obtained for all sixteen stereoisomers of 3,7,9-trimethyltridecan-2-ol and for the four 3-methylpentadecan-2-ol stereoisomers. For 3,7-dimethyltridecan-2-ol, 3,7-dimethyltetradecan-2-ol and 3,7-dimethylpentadecan-2-ol baseline separation was obtained for 6 of the possible 8 stereoisomers. When a mixture of 16 stereoisomers of 3,7,11-trimethyltridecan-2-ol was tested, baseline separation of 7 peaks out of 16 possible was obtained. The investigated alcohols are pheromone precursors for some pine sawfly species that are severe defoliators of pine. Females from several Diprion, Neodiprion, Macrodiprion, Microdiprion, and Gilpinia species emit esters of such secondary alcohols as sex pheromones that attract males for mating. To quantify the small amounts of the precursor alcohol and its stereoisomeric composition found in whole body extracts from female pine sawflies, a purification method was optimized. An extract of 20 females of D. pini contained about 8 ng of (2S,3R,7R)-3,7-dimethyltridecan-2-ol per female, and three extracts of 18, 20, and 90 females of N. sertifer contained between 5 and 13 ng of (2S,3S,7S)-3,7-dimethylpentadecan-2-ol per female.     

Fish Oil Supplementation During Late Pregnancy Does Not Influence Plasma Lipids or Lipoprotein Levels in Young Adult Offspring

Nutritional influences on cardiovascular disease operate throughout life. Studies in both experimental animals and humans have suggested that changes in the peri- and early post-natal nutrition can affect the development of the various components of the metabolic syndrome in adult life. This has lead to the hypothesis that n-3 fatty acid supplementation in pregnancy may have a beneficial effect on lipid profile in the offspring. The aim of the present study was to investigate the effect of supplementation with n-3 fatty acids during the third trimester of pregnancy on lipids and lipoproteins in the 19-year-old offspring. The study was based on the follow-up of a randomized controlled trial from 1990 where 533 pregnant women were randomized to fish oil (n = 266), olive oil (n = 136) or no oil (n = 131). In 2009, the offspring were invited to a physical examination including blood sampling. A total of 243 of the offspring participated. Lipid values did not differ between the fish oil and olive oil groups. The relative adjusted difference (95% confidence intervals) in lipid concentrations was −3% (−11; 7) for LDL cholesterol, 3% (−3; 10) for HDL cholesterol, −1% (−6; 5) for total cholesterol,−4% (−16; 10) for TAG concentrations, 2%(−2; 7) for apolipoprotein A1, −1% (−9; 7) for apolipoprotein B and 3% (−7; 15) in relative abundance of small dense LDL. In conclusion, there was no effect of fish oil supplementation during the third trimester of pregnancy on offspring plasma lipids and lipoproteins in adolescence.     

A computational study of oscillatory extinction of spherical diffusion flames

The transient behavior of burner-supported spherical diffusion flames was studied in the transport-induced limit of low mass flow rate and the radiation-induced limit of high mass flow rate which characterize the isola response of flame extinction. Oscillatory instability was observed near both steady-state extinction limits. The oscillation typically grows in amplitude until it becomes large enough to extinguish the flame. The oscillatory behavior was numerically observed using detailed chemistry and transport for methane (50%CH₄/50%He into 21%O₂/79%He) and hydrogen (100% H₂ into 21%O₂/79%He) diffusion flames where the fuel was issued from a point source, and helium was selected as an inert to increase the Lewis number, facilitating the onset of oscillation. In both methane and hydrogen flames, the oscillation always leads to extinction, and no limit cycle behavior was found. The growth rate of the oscillation was found to be slow enough under certain conditions to allow the flame to oscillate for over 450 s, suggesting that such oscillations can possibly be observed experimentally. For the hydrogen flames, however, the frequency of oscillation near the transport-induced limit is much larger, approximately 60 Hz as compared to 0.35 Hz for the methane flame, and the maximum amplitude of temperature oscillations was about 5 K. The distinctively different structures of the hydrogen and methane flames suggest that while both instabilities are thermal-diffusive in origin, oscillations in the hydrogen flames resemble those of premixed flames, while oscillations in the methane flames are non-premixed in character.     

Material Selection for Cryogenic Support Structures

Design specifications for the support structures of low temperature instrumentation often call for low thermal conductivity between temperature stages, high stiffness, and specific load bearing capabilities. While overall geometric design plays an important role in both overall stiffness and heat conduction between stages, material selection can affect a structure’s properties significantly. In this contribution, we suggest and compare several alternative materials to the current standard materials for building cryogenic support structures.     

Explicit strategies for incompressible fluid‐structure interaction problems: Nitsche type mortaring versus Robin–Robin coupling

We discuss explicit coupling schemes for fluid‐structure interaction problems where the added mass effect is important. In this paper, we show the close relation between coupling schemes by using Nitsche's method and a Robin–Robin type coupling. In the latter case, the method may be implemented either using boundary integrals of the stresses or the more conventional discrete lifting operators. Recalling the explicit method proposed in Comput. Methods Appl. Mech. Engrg. 198(5‐8):766–784, 2009, we make the observation that this scheme is stable under a hyperbolic type CFL condition, but that optimal accuracy imposes a parabolic type CFL conditions because of the splitting error. Two strategies to enhance the accuracy of the coupling scheme under the hyperbolic CFL‐condition are suggested, one using extrapolation and defect‐correction and one using a penalty‐free non‐symmetric Nitsche method. Finally, we illustrate the performance of the proposed schemes on some numerical examples in two and three space dimensions. Copyright © 2013 John Wiley & Sons, Ltd.     

Tailoring the Mechanical Properties of High‐Aspect‐Ratio Carbon Nanotube Arrays using Amorphous Silicon Carbide Coatings

The porous nature of carbon nanotube (CNT) arrays allows for the unique opportunity to tailor their mechanical response by the infiltration and deposition of nanoscale conformal coatings. Here, we fabricate novel photo‐lithographically defined CNT pillars that are conformally coated with amorphous silicon carbide (a‐SiC) to strengthen the interlocking of individual CNTs at junctions using low pressure chemical vapor deposition (LPCVD). We further quantify the mechanical response by performing flat‐punch nanoindentation measurements on coated CNT pillars with various high‐aspect‐ratios. We discovered new mechanical failure modes of coated CNT pillars, such as “bamboo” and brittle‐like composite rupture as coating thickness increases. Furthermore, a significant increase in strength and modulus is achieved. For CNT pillars with high aspect ratio (1:10) and coating thickness of 21.4 nm, the compressive strength increases by an order of magnitude of 3, towards 1.8 GPa (from below 1 MPa for uncoated CNT pillars) and the elastic modulus increases towards 125 GPa. These results show that our coated CNT pillars, which can serve as vertical interconnects and 3D super‐capacitors, can be transformed into robust high‐aspect‐ratio 3D‐micro architectures with semiconductor device compatible processes.