Triacylglycerol profiling of microalgae strains for biofuel feedstock by liquid chromatography-high-resolution mass spectrometry

Biofuels from photosynthetic microalgae are quickly gaining interest as a viable carbon-neutral energy source. Typically, characterization of algal feedstock involves breaking down triacylglycerols (TAG) and other intact lipids, followed by derivatization of the fatty acids to fatty acid methyl esters prior to analysis by gas chromatography (GC). However, knowledge of the intact lipid profile could offer significant advantages for discovery stage biofuel research such as the selection of an algal strain or the optimization of growth and extraction conditions. Herein, lipid extracts from microalgae were directly analyzed by ultra-high pressure liquid chromatography–mass spectrometry (UHPLC-MS) using a benchtop Orbitrap mass spectrometer. Phospholipids, glycolipids, and TAGs were analyzed in the same chromatographic run, using a combination of accurate mass and diagnostic fragment ions for identification. Using this approach, greater than 100 unique TAGs were identified over the six algal strains studied and TAG profiles were obtained to assess their potential for biofuel applications. Under the growth conditions employed, Botryococcus braunii and Scenedesmus obliquus yielded the most comprehensive TAG profile with a high abundance of TAGs containing oleic acid.     

Spontaneous membrane-translocating peptides by orthogonal high-throughput screening

Combinatorial peptide chemistry and orthogonal high-throughput screening were used to select peptides that spontaneously translocate across synthetic lipid bilayer membranes without permeabilization. A conserved sequence motif was identified that contains several cationic residues in conserved positions in an otherwise hydrophobic sequence. This 9-residue motif rapidly translocates across synthetic multibilayer vesicles and into cells while carrying a large polar dye as a "cargo" moiety. The extraordinary ability of this family of peptides to spontaneously translocate across bilayers without an energy source of any kind is distinctly different from the behavior of the well-known, highly cationic cell-penetrating peptides, such as the HIV tat peptide, which do not translocate across synthetic bilayers, and enter cells mostly by active endocytosis. Peptides that translocate spontaneously across membranes have the potential to transform the field of drug design by enabling the delivery of otherwise membrane-impermeant polar drugs into cells and tissues. Here we describe the chemical tools needed to rapidly identify spontaneous membrane translocating peptides.     

Electron-transfer reactions at the plasma-liquid interface

Electrochemical reactions are normally initiated in solution by metal electrodes such as Pt, which are expensive and limited in supply. In this Communication, we demonstrate that an atmospheric-pressure microplasma can act as a gaseous, metal-free electrode to mediate electron-transfer reactions in aqueous solutions. Ferricyanide is reduced to ferrocyanide by plasma electrons, and the reduction rate is found to depend on discharge current. The ability to initiate and control electrochemical reactions at the plasma-liquid interface opens a new direction for electrochemistry based on interactions between gas-phase electrons and ionic solutions.     

Hydride as a leaving group in the reaction of pinacolborane with halides under ambient Grignard and Barbier conditions. One-pot synthesis of alkyl, aryl, heteroaryl, vinyl, and allyl pinacolboronic esters

Grignard reagents (aliphatic, aromatic, heteroaromatic, vinyl, or allylic) react with 1 equiv of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (pinacolborane, PinBH) at ambient temperature in tetrahydrofuran (THF) to afford the corresponding pinacolboronates. The initially formed dialkoxy alkylborohydride intermediate quickly eliminates hydridomagnesium bromide (HMgBr) and affords the product boronic ester in very good yield. Hydridomagnesium bromide (HMgBr) in turn disproportionates to a 1:1 mixture of magnesium hydride (MgH(2)) and magnesium bromide (MgBr(2)) on addition of pentane to the reaction mixture. DFT calculations (Gaussian09) at the B3LYP/6-31G(d) level of theory show that disproportionation of HMgBr to MgH(2) and MgBr(2) is viable in the coordinating ethereal solvents. This reaction also can be carried out under Barbier conditions, where the neat PinBH is added to the flask prior to the in situ formation of Grignard reagent from the corresponding organic halide and magnesium metal. Pinacolboronic ester synthesis under Barbier conditions does not give Wurtz coupling side products from reactive halides, such as benzylic and allylic halides. The reaction between PinBH and various Grignard reagents is an efficient, mild, and general method for the synthesis of pinacolboronates.     

Temperature-controlled 'breathing' of carbon dioxide bubbles

We report a microfluidic (MF) approach to studies of temperature mediated carbon dioxide (CO(2)) transfer between the gas and the liquid phases. Micrometre-diameter CO(2) bubbles with a narrow size distribution were generated in an aqueous or organic liquid and subsequently were subjected to temperature changes in the downstream channel. In response to the cooling-heating-cooling cycle the bubbles underwent corresponding contraction-expansion-contraction transitions, which we term 'bubble breathing'. We examined temperature-controlled dissolution of CO(2) in four exemplary liquid systems: deionized water, a 0.7 M aqueous solution of NaCl, ocean water extracted from Bermuda coastal waters, and dimethyl ether of poly(ethylene glycol), a solvent used in industry for absorption of CO(2). The MF approach can be extended to studies of other gases with a distinct, temperature-dependent solubility in liquids.     

Simultaneous quantitative flow measurement using PIV on both sides of the air–water interface for breaking waves

An experimental method for simultaneously measuring the velocity fields on the air and water side of unsteady breaking waves is presented. The method includes a novel technique for seeding the air flow such that the air velocity can be resolved in the absence of wind. Low density particles that have large Stokes drag and ability to respond to high-frequency flow fluctuations are used to seed the air flow. Multi-camera, multi-laser particle image velocimetry setups are applied to small-scale unsteady breaking waves, yielding fully time-resolved velocity fields. The surface tension of the fluid is altered and controlled to form spilling breaking waves. Results for the velocity and vorticity fields of representative spilling breakers, which show shedding of an air-side vortex and well-documented generation of water-side vorticity, are presented and discussed.     

Subitising activity relative to units construction: a case study

Subitising, a quick apprehension of the numerosity of a small set of items, has been found to change from an individual's reliance on perceptual to conceptual processes. In this study, we utilised a constructivist teaching experiment methodology to investigate how the subitising activity of one preschool student, Amy, related to her construction of prenumerical units. Subitising and counting tasks were designed to assess and perturb Amy's thinking relative to her construction of units, and to observe changes in Amy's activity associated with the different tasks. Findings indicate that as Amy's subitising activity changed from perceptual to conceptual, she constructed subitised motor units and subitised figurative units. Implications of this study suggest that the construction of subitised units may support young children's later development of arithmetic units.     

Ultrahigh pressure equation of state of tantalum to 310 GPa

ABSTRACT

The isothermal compression of transition metal tantalum (Ta) was studied in a diamond anvil cell by X-ray diffraction utilizing rhenium (Re) and gold (Au) as internal X-ray pressure standards. The Re pressure marker was employed during non-hydrostatic compression to pressures up to 310?GPa while the Au pressure marker was used during quasi-hydrostatic compression in a neon pressure-transmitting medium to 80?GPa. Two ultra-high pressure experiments were conducted on Ta and Re mixtures utilizing focused-ion beam machined toroidal diamond anvils with central flats varying from 8 microns to 16 microns in diameter. The Ta metal was observed to be stable in the body-centered-cubic phase to a volume compression V/V₀?=?0.581. The measured equations of state (EOS) of Ta using two different calibrations of the Re pressure marker are compared with the ambient temperature isotherm derived from shock compression data. We provide a detailed analysis of EOS fit parameters for Ta under quasi-hydrostatic and non-hydrostatic conditions.     

Converging flow of a viscoelastic liquid

Two-dimensional creeping sink flow of a Maxwell fluid is an accurate approximation to a bounded converging flow of contraction ratio at least 5 : 1 and covergence half-angles of up to 45°. In this range, a perturbation expansion in Weissenberg number can be used over most of the flow field in the range where stable processing can be carried out.