A Simple Primary Amide for the Selective Recovery of Gold from Secondary Resources

Waste electrical and electronic equipment (WEEE) such as mobile phones contains a plethora of metals of which gold is by far the most valuable. Herein a simple primary amide is described that achieves the selective separation of gold from a mixture of metals typically found in mobile phones by extraction into toluene from an aqueous HCl solution; unlike current processes, reverse phase transfer is achieved simply using water. Phase transfer occurs by dynamic assembly of protonated and neutral amides with [AuCl₄]^? ions through hydrogen bonding in the organic phase, as shown by EXAFS, mass spectrometry measurements, and computational calculations, and supported by distribution coefficient analysis. The fundamental chemical understanding gained herein should be integral to the development of metal‐recovery processes, in particular through the use of dynamic assembly processes to build complexity from simplicity.     

Synthesis and absolute configuration of a constitutionally-new [5.6] spiroacetal from B. tryoni (Queensland fruit fly)

A novel spiroacetal, (2S,6R,8S)-2-methyl-8-ethyl-1,7-dioxaspiro[5.6]dodecane (1), has been identified from the volatile secretions of female B. tryoni by mass spectral analysis and synthesis of an authentic, enantioenriched sample.     

Structure conditioned velocity statistics in a high pressure swirl flame

A piloted, partially premixed, liquid-fueled swirl burner is operated at high pressure (1 MPa). High-speed (6 KHz) stereoscopic PIV is used to investigate the characteristics of the stagnation line separating the pilot jet and the central recirculation zone (CRZ) with varying pilot-main ratio and global equivalence ratio. The mean curvature of the stagnation line displayed a large spatial scale pattern that was present for all operating conditions. All three components of velocity, in-plane shear, and swirling strength are conditioned upon the instantaneous stagnation line. Mean distributions of the velocity normal to the stagnation line show that velocity is oriented towards the CRZ when the stagnation line is found nearer the centerline of the combustor. The conditioned out-of-plane velocity (w) shows a distinct concentration of large mean and fluctuation RMS values towards the center of the measurement domain. Varying fuel flow does not significantly change this spatial structure, only the magnitudes of the w statistics. The in-plane shear stress was the largest for the pilot biased condition as a stronger shear layer develops. For the leanest flame, large fluctuation RMS values of shear stress were confined to a region where the pilot jet begins to interact more heavily with the main jet. Operating with less pilot fuel flow enhanced the mean conditional swirling strength indicating that the pilot shear layer was shedding more intense eddies. Disregarding spatial relations, a scatter plot of w, shear stress, and swirling strength displayed trends between the variables. The largest swirling strength values coincide with highest magnitude shear stresses and the widest range of w. These conditioned statistics highlight how certain aspects of the combustor flow field are invariant with fuel distribution. This is desirable for aeropropulsive combustors that must maintain stable ignition from a range of conditions from landing/take-off to cruise.     

Micellar spheres in a high frequency oscillatory field

The viscoelasticity of aqueous micellar solutions of two oxyethylene/oxybutylene block copolymers (E(92)B(18) and B(20)E(510)) has been investigated using a torsional resonator operated at 26 kHz. For both systems considered, values of the dynamic viscosity (eta'(infinity)) point to partial draining of the micellar corona induced by the high-frequency oscillatory field. At low effective volume fractions, values of the elastic modulus (G'(infinity)) indicate that the repulsive interactions between micelles can be modeled by a power law function u(r) proportional to 1/r(nu) with exponents close to 13 and 6 for copolymers E(92)B(18) and B(20)E(510) respectively. At a critical copolymer concentration (c*) plots of log(G'(infinity)) against log(c) deviate from the straight lines established at low concentrations, implying that the systems undergo ergodic/nonergodic transitions.     

Rheological behavior of aqueous micellar solutions of a triblock copolymer of ethylene oxide and 1,2-butylene oxide: B10E410B10

A triblock copolymer of ethylene oxide and 1,2-butylene oxide, denoted B10E410B10, was prepared by sequential oxyanionic polymerization and characterized by 13C NMR spectroscopy and gel permeation chromatography. Micellization and the formation of micelle clusters in dilute aqueous solution, the latter a consequence of micelle bridging, was confirmed by dynamic light scattering, and average association numbers of the micelles were determined by static light scattering for T = 20-40 degrees C. The frequency dependence of the dynamic storage and loss moduli was investigated for solutions in the range of 5-20 wt %. Comparison with results for poly(oxyethylene) dialkyl ethers (10 wt %, T = 25 degrees C) indicated that the viscoelasticity of a copolymer with terminal B10 hydrophobic blocks was roughly equivalent to one with terminal C14 alkyl chains. The temperature dependence of the modulus was investigated for 15 wt % solutions at T = 5-40 degrees C. Superposition of the data led, via an Arrhenius plot, to an activation energy for the relaxation process of -40 kJ mol(-1). The negative value contrasts with the positive values found for poly(oxyethylene) dialkyl ethers and related HEUR copolymers with urethane-linked terminal alkyl chains. This difference is attributed to the block-length distribution in copolymer B10E410B10, whereby the activation energy of the relaxation process has a positive contribution from the disengagement of B blocks from micelles but a negative contribution from micellization. The negative value of the activation energy for solutions of B10E410B10 was confirmed by determining the temperature dependence of the zero-shear viscosity of its 15 wt % solution.     

Measurement and simulations of hollow atom X-ray spectra of solid-density relativistic plasma created by high-contrast PW optical laser pulses

K-shell spectra of solid Al excited by petawatt picosecond laser pulses have been investigated at the Vulcan PW facility. Laser pulses of ultrahigh contrast with an energy of 160 J on the target allow studies of interactions between the laser field and solid state matter at 10²⁰ W/cm². Intense X-ray emission of KK hollow atoms (atoms without n = 1 electrons) from thin aluminum foils is observed from optical laser plasma for the first time. Specifically for 1.5 μm thin foil targets the hollow atom yield dominates the resonance line emission. It is suggested that the hollow atoms are predominantly excited by the impact of X-ray photons generated by radiation friction to fast electron currents in solid-density plasma due to Thomson scattering and bremsstrahlung in the transverse plasma fields. Numerical simulations of Al hollow atom spectra using the ATOMIC code confirm that the impact of keV photons dominates the atom ionization. Our estimates demonstrate that solid-density plasma generated by relativistic optical laser pulses provide the source of a polychromatic keV range X-ray field of 10¹⁸ W/cm² intensity, and allows the study of excited matter in the radiation-dominated regime. High-resolution X-ray spectroscopy of hollow atom radiation is found to be a powerful tool to study the properties of high-energy density plasma created by intense X-ray radiation.     

Aromatic interactions impact ligand binding and function at serotonin 5-HT2C G protein-coupled receptors: receptor homology modelling,ligand docking,and molecular dynamics results validated by experimental studies

The serotonin (5-hydroxytryptamine, 5-HT) 5-HT₂ G protein-coupled receptor (GPCR) family consists of types 2A, 2B, and 2C that share ～75% transmembrane (TM) sequence identity. Agonists for 5-HT_2C receptors are under development for psychoses; whereas, at 5-HT_2A receptors, antipsychotic effects are associated with antagonists – in fact, 5-HT_2A agonists can cause hallucinations and 5-HT_2B agonists cause cardiotoxicity. It is known that 5-HT_2A TM6 residues W6.48, F6.51, and F6.52 impact ligand binding and function; however, ligand interactions with these residues at the 5-HT_2C receptor have not been reported. To predict and validate molecular determinants for 5-HT_2C-specific activation, results from receptor homology modelling, ligand docking, and molecular dynamics simulation studies were compared with experimental results for ligand binding and function at wild type and W6.48A, F6.51A, and F6.52A point-mutated 5-HT_2C receptors.     

Microfluidically-unified cell culture, sample preparation, imaging and flow cytometry for measurement of cell signaling pathways with single cell resolution

We have developed a microfluidic platform that enables, in one experiment, monitoring of signaling events spanning multiple time-scales and cellular locations through seamless integration of cell culture, stimulation and preparation with downstream analysis. A combination of two single-cell resolution techniques-on-chip multi-color flow cytometry and fluorescence imaging provides multiplexed and orthogonal data on cellular events. Automated, microfluidic operation allows quantitatively- and temporally-precise dosing leading to fine time-resolution and improved reproducibility of measurements. The platform was used to profile the toll-like receptor (TLR4) pathway in macrophages challenged with lipopolysaccharide (LPS)-beginning with TLR4 receptor activation by LPS, through intracellular MAPK signaling, RelA/p65 translocation in real time, to TNF-α cytokine production, all in one small macrophage population (< 5000 cells) while using minute reagent volume (540 nL/condition). The platform is easily adaptable to many cell types including primary cells and provides a generic platform for profiling signaling pathways.