Arachidonic, eicosapentaenoic, and biosynthetically related fatty acids in the seed lipids from a primitive gymnosperm, Agathis robusta

The fatty acid composition of the seeds from Agathis robusta, an Australian gymnosperm (Araucariaceae), was determined by a combination of chromatographic and spectrometric techniques. These enabled the identification of small amounts of arachidonic (5,8,11,14–20∶4) and eicosapentaenoic (5,8,11,14,17–20∶5) acid for the first time in the seed oil of a higher plant. They were apparently derived from γ-linolenic (6,9,12–18∶3) and stearidonic (6,9,12,15–18∶4) acids, which were also present, via chain elongation and desaturation, together with other expected biosynthetic intermediates [bis-homo-γ-linolenic (8,11,14–20∶3) and bishomo-stearidonic (8,11,14,17–20∶4) acids]. Also present were a number of C₂₀ fatty acids, known to occur in most gymnosperm families, i.e., 5,11–20∶2, 11,14–20∶2 (bishomo-linoleic), 5,11,14–20∶3 (sciadonic), 11,14,17–20∶3 (bishomo-α-linolenic), and 5,11,14,17–20∶4 (juniperonic) acids. In contrast to most other gymnosperm seed lipids analyzed so far, A. robusta seed lipids did not contain C₁₈ Δ5-desaturated acids [i.e., 5,9–18∶2 (taxoleic), 5,9,12–18∶3 (pinolenic), or 5,9,12,15–18∶4 (coniferonic)]. These structures support the simultaneous existence of Δ6- and Δ5-desaturase activities in A. robusta seeds. The Δ6-ethylenic bond is apparently introduced into C₁₈ polyunsaturated acids, whereas the Δ5-ethylenic bond is introduced into C₂₀ polyunsaturated acids. A general metabolic pathway for the biosynthesis of unsaturated fatty acids in gymnosperm seeds is proposed. When compared to Bryophytes, Pteridophytes (known to contain arachidonic and eicosapentaenoic acids), and species from other gymnosperm families (without such acids), A. robusta appears as an “intermediate,” with the C₁₈ Δ6-desaturase/C₁₈→C₂₀ elongase/C₂₀ Δ5-desaturase system in common with the former subphyla, and the unsaturated C₁₈→C₂₀ elongase/C₂₀ Δ5-desaturase system specific to gymnosperms. The following hypothetical evolutionary sequence for the C₁₈ Δ6/Δ5-desaturase class in gymnosperm seeds is suggested: Δ6 (initial)→Δ6/Δ5 (intermediate)→Δ5 (final).     

Gold nanoparticle colorants as traditional ceramic glaze alternatives

Historically, Roman stained glass has been a standard for high‐temperature color stability since biblical times but was not properly characterized as emission from nanoparticle plasmon resonance until the 1990s. The methods under which it was created have been lost, but some efforts have recently been made to recreate these properties using gold nanoparticle inks on glassy surfaces. This body of work employs gold nanoparticle systems ranging from 0.015% to 0.100% (wt/wt), suspended in a clear glaze body. The glazes are fired with traditional ceramic methods—in both gas reduction and electric oxidation kilns—in which nanoparticles are retained and can be imaged via TEM. Various colors intensities are reported in addition to changes in nanoparticle size after application and firing. The nanoparticle glazes are compared to traditional red glazes, highlighting the significantly lower metal loading required (5%‐10% for traditional glazes vs 0.100% for gold (wt/wt)), therein. Finally, proof of concept is provided with a functional gold nanoparticle mug, fired in reduction, that costs roughly 0.98$ USD in gold used.     

Achievement of energy focus for distance-of-flight mass spectrometry with constant momentum acceleration and an ion mirror

Distance-of-flight mass spectrometry (DOF-MS) has not yet been implemented, though it has many potential advantages in a variety of applications. Impeding the implementation of DOF-MS is the development of the required array detectors and working out the equivalents to the focusing methods now used in time-of-flight (TOF) mass analyzers. Ideally, a batch of ions composed of a variety of m/z values, despite initial distributions of space and energy, would be spatially focused at their respective flight distances at the same time. First-order energy focusing, including ion turnaround, is shown to be accomplished by the use of an ion mirror in conjunction with constant momentum acceleration of the initial ion packet. The initial spatial dispersion is maintained throughout the flight path. With zero initial spatial ion spread, energy focusing to achieve resolutions in the tens of thousands is shown to be feasible with ions from the elemental and isotope ratio mass regions through the extremely high m/z range. With moderate spatial spread taken into account, the DOF-MS approach is shown to achieve resolutions competitive with quadrupole and ion trap mass analyzers. Advantages of DOF-MS include all the advantages of TOF-MS plus simpler detector electronics and the improved signal-to-noise ratio and dynamic range afforded by array detection.     

Effect of fatty acid positional distribution and triacylglycerol composition on lipid by-products formation during heat treatment: I. polymer formation

Effects of the fatty acid positional distribution and of the triacylglycerol (TG) composition on polymerization of TG during heat treatment were studied. Diacid TG molecules, acylated only with linoleic acid or linolenic acid along with palmitic acid, and positioned either in the central position (PLP and PLnP, respectively) or in one of the two outer positions (PPL and PPLn, respectively) were synthesized. Monoacid TG, i.e., trilinolein and trilinolenin, were also synthesized and mixed with tripalmitin in a 1:2 ratio. These model TG were also compared to TG models that consisted of a canola oil and its randomized counterpart, whose fatty acid positional distribution and TG composition were determined by means of high-performance liquid chromatography (HPLC). After heating, the polymer content and composition were evaluated by HPLC-size exclusion chromatography. Both pure TG and the canola oil models showed that acylation of polyunsaturated acids in the central position was protective against polymerization, although the effect was mainly observed with linolenic acid. The synthetic-TG study showed that the monoacid TG species exhibited higher sensitivity toward polymerization than the diacid species. The slight differences in the TG species between both canola oils did not allow observation of such a relationship with regard to TG composition.     

Structures,practical sources (gymnosperm seeds), gas‐liquid chromatographic data (equivalent chain lengths), and mass spectrometric characteristics of all‐cis Δ5‐olefinic acids

In view of the increasing interest of lipid researchers in the biological effects of all‐cis Δ5‐unsaturated polymethylene‐interrupted fatty acids (Δ5‐UPIFA) from vegetable origin, this paper is concerned with their occurrence in practical sources (gymnosperm seeds), structures, and identification by gas‐liquid chromatography (GLC) and mass spectrometry (MS). The use of equivalent chain lengths (ECL) determined by calculations based on available standards, in close agreement with data determined with easily available commercial gymnosperm seeds specific for each Δ5‐UPIFA, allows identification of all Δ5‐UPIFA. These tentative identifications are supported by GLC‐MS of the appropriate (4, 4‐dimethyloxazoline and picolinyl ester) derivatives. ECL are particularly useful to identify Δ5‐UPIFA in tissue lipids from animals experimentally fed oils containing these acids, with no interference with polyunsaturated fatty acids of endogenous origin.     

Effect of thermal conditioning on the initiation threshold of secondary high-explosives

While most performance metrics of high-explosive (HE) based devices like detonation velocity, detonation pressure, and energy output are expected to degrade over time, the evolution of initiation threshold appears less clear, with claims of both increasing and decreasing trends in threshold having been made in the literature. This work analyzes D-optimally designed sequential binary test data for a few thermally conditioned porous-powder and polymer-bonded HE initiator systems using a Bayesian likelihood method employing the probit regression model. We find that in most cases the initiation threshold decreases (i. e., sensitivity increases) upon accelerated thermal conditioning. However, such results are nuanced and influenced by factors like the contact area of initiating stimulus, HE characteristics like density and specific surface area, as well as possible thermally induced changes to other materials and interfaces involved.     

Growth of InGaN quantum dots with AlGaN barrier layers via modified droplet epitaxy

The growth of c-plane InGaN quantum dots via modified droplet epitaxy with AlGaN barrier layers is reported. The growth of the AlGaN layer underlying the InGaN quantum dot layer was carried out under H₂ at 1050 °C, while the capping AlGaN layer was grown at the same temperature (710 °C) and using the same carrier gas (N₂) as that used to grow the InGaN quantum dot layer to prevent decomposition of the InGaN. Atomic force microscopy of InGaN epilayers grown and annealed on high temperature AlGaN using identical growth conditions used for the quantum dot samples highlighted a narrower distribution of nanostructure heights than that obtained for similar growth on GaN. Scanning transmission electron microscopy (STEM) imaging combined with energy dispersive X-ray (EDX) analysis revealed the presence of a thin high aluminium content layer at the surface of both AlGaN layers, which is believed to be related to loss of Ga during temperature ramping processes. Micro-photoluminescence studies carried out at low temperature revealed near resolution-limited peaks while time-resolved measurements on these peaks demonstrated mono-exponential decay times between 1 and 4 ns, showing that quantum dots had successfully been formed between the AlGaN barriers. Temperature-dependant measurement of the emission lines revealed that quenching of the peak often occurred at ∼60–70 K, with some of the peaks exhibiting significant line broadening whilst others remained narrow.     

Surface functionalization of silver nanoparticles: novel applications for insect vector control

Every day, people and animals contract debilitating and life threatening diseases due to bites from infected flies, ticks, and mosquitoes. The current methods utilized to fight against these diseases are only partially effective or safe for humans and animals. When it comes to insect vector control, a conceptual paradigm shift is urgently needed. This work proposes a novel synthetic scheme to produce a nanoparticle-pesticide core-shell conjugate to be used as an active agent against arthropod vectors, such as mosquitoes. As a proof of concept, we conjugated nanosilver to the pyrethroid pesticide deltamethrin. First, electron microscopy and Fourier transform infrared spectroscopy verified the presence of a 15 nm nanosilver core surrounded by deltamethrin. Second, when the conjugate was exposed to mosquitoes for a 24 h bioassay, mortality was observed at 9 × 10(-4) M. Silver was detected in the hemolymph of mosquitoes exposed to the conjugate. We concluded that the newly developed nanoconjugate did not inactivate the primary function of the pesticide and was effective in killing mosquitoes at low concentrations. These results demonstrate the potential to use nanoparticle surfaces to kill insects, specifically vectors of human pathogens.