Automated on-line dispersive liquid–liquid microextraction based on a sequential injection system

A novel approach for sequential injection-dispersive liquid–liquid microextraction (SI-DLLME) has been suggested. The method is based on the aspiration and mixing of a sample and all required aqueous reagents in the holding coil of an SIA system, delivering it into a conical tube and adding in a mixture of extraction solvent, auxiliary solvent and disperser solvent at high flow rate, resulting in the formation of a cloudy state and the extraction of an analyte. The mixture of extraction and auxiliary solvent is immiscible with water and has a density significantly higher than that of water; consequently, the resulting fine droplets in the mixture, which contain the extracted analyte, are self-sedimented in a short time at the bottom of conical tube. Thus, no centrifugation and no use of a microcolumn are required for separation of the extraction phase. Afterwards, the extracted analyte is aspirated and transferred to a micro-volume Z-flow cell, and the absorbance is measured.The performance of the suggested approach is demonstrated by the SI-DLLME of thiocyanate ions in the form of ion associate with dimethylindocarbocyanine reagent, followed by spectrophotometric detection. A mixture of amyl acetate (as extraction solvent), tetrachloromethane (as auxiliary solvent) and acetonitrile (as disperser solvent) was selected for the DLLME procedure. The appropriate experimental conditions for conventional DLLME and automated SI-DLLME were investigated. The analytical performance of both these procedures was compared. The absorbance of the colored extracts at wavelength 555 nm obeys Beer's law in the range of 3.13–28.2 for conventional DLLME and 0.29–5.81 mg L^? 1 of SCN for SI-DLLME, and the limit of detection, calculated from a blank test based on 3 s, is 0.110 for conventional DLLME and 0.017 mg L^? 1 for SI-DLLME.     

Lie derived length and involutions in group algebras

Let $G$ be a group such that the set of $p$-elements of $G$ forms a finite nonabelian subgroup, where $p$ is an odd prime, and let $F$ be a field of characteristic $p$. In this paper we prove that the lower bound of the Lie derived length of the group algebra $FG$ given by Shalev in [11] is also a lower bound for the Lie derived length of the set of symmetric elements of $FG$ for every involution which is linear extension of an involutive anti-automorphism of $G$. Furthermore, we provide counterexamples to the interesting cases which are not covered by the main theorem.     

Anisotropic turbulent spectra in the terrestrial magnetosheath as seen by the cluster spacecraft

Here we report the first three-dimensional spatial spectrum of the low frequency magnetic turbulence obtained from the four Cluster spacecraft in the terrestrial magnetosheath close to the magnetopause. We show that the turbulence is compressible and dominated by mirror structures, its energy is injected at a large scale kp approximately 0.3 (l approximately 2000 km) via a mirror instability well predicted by linear theory, and cascades nonlinearly and unexpectedly up to kp approximately 3.5 (l approximately 150 km), revealing a new power law in the inertial range not predicted by any turbulence theory, and its strong anisotropy is controlled by the static magnetic field and the magnetopause normal.     

Use of PLL-g-PEG in micro-fluidic devices for localizing selective and specific protein binding

By utilizing flow-controlled PLL-g-PEG and PLL-g-PEGbiotin modification of predefined regions of a poly(dimethylsiloxane) (PDMS) micro-fluidic device, with an intentionally chosen large (approximately 1 cm2) internal surface area, we report rapid (10 min), highly localized (6 x 10(-6) cm2), and specific surface-based protein capture from a sample volume (100 microL) containing a low amount of protein (160 attomol in pure buffer and 400 attomol in serum). The design criteria for this surface modification were achieved using QCM-D (quartz crystal microbalance with energy dissipation monitoring) of serum protein adsorption onto PLL-g-PEG-modified oxidized PDMS. Equally good, or almost as good, results were obtained for oxidized SU-8, Topas, and poly(methyl metacrylate) (PMMA), demonstrating the generic potential of PLL-g-PEG for surface modification in various micro-fluidic applications.     

Hydrogen release from mixtures of lithium borohydride and lithium amide: a phase diagram study

We recently reported the synthesis of a new quaternary hydride in the lithium-boron-nitrogen-hydrogen quaternary phase diagram with the approximate composition LiB0.33N0.67H2.67 having a theoretical hydrogen content of 11.9 wt %. This new compound forms by the reaction of appropriate amounts of lithium amide (LiNH2) and lithium borohydride (LiBH4) and releases greater than 10 wt % hydrogen when heated. A small amount of ammonia, 2-3 mol % of the generated gas, is also released. We now report a study of hydrogen and ammonia release from the series of reactant mixtures (LiNH2)x(LiBH4)1-x, where x=0.667 corresponds to the composition LiB0.33N0.67H2.67. We measured hydrogen and ammonia release amounts as a function of composition and found that maximum hydrogen and minimum ammonia release do occur for x=0.667. We also present evidence for an additional new quaternary phase and for two possibly metastable phases in this system.     

Effect of barium loading on the desulfation of Pt-BaO/Al2O3 studied by H2 TPRX, TEM, sulfur K-edge XANES, and in situ TR-XRD

Desulfation processes were investigated over sulfated Pt-BaO/Al2O3 with different barium loading (8 and 20 wt %) by using H2 temperature programmed reaction (TPRX), transmission electron microscope (TEM) with energy dispersive spectroscopy (EDS), sulfur K-edge X-ray absorption near-edge spectroscopy (XANES), and in situ time-resolved X-ray diffraction (TR-XRD) techniques. Both sulfated samples (8 and 20 wt %) form sulfate species (primarily BaSO4) as evidenced by S K-edge XANES and in situ TR-XRD. However, the desulfation behavior is strongly dependent on the barium loading. Sulfated Pt-BaO8/Al2O3, consisting predominantly of surface BaO/BaCO3 species, displays more facile desulfation by H2 at lower temperatures than sulfated Pt-BaO20/Al2O3, a material containing primarily bulk BaO/BaCO3 species. Therefore, after desulfation with H2 up to 1073 K, the amount of the remaining sulfur species on the former, mostly as BaS, is much less than that on the latter. This suggests that the initial morphology differences between the two samples play a crucial role in determining the extent of desulfation and the temperature at which it occurs. It is concluded that the removal of sulfur is significantly easier at lower barium loading. This finding can potentially be important in developing more sulfur resistant LNT catalyst systems.     

Uniformly Quasiregular Maps on the Compactified Heisenberg Group

We show the existence of a non-injective uniformly quasiregular mapping acting on the one-point compactification $\bar{ {\mathbb{H}}}^{1}={\mathbb{H}}^{1}\cup\{\infty\}$ of the Heisenberg group ?¹ equipped with a sub-Riemannian metric. The corresponding statement for arbitrary quasiregular mappings acting on sphere ${\mathbb{S}}^{n} $ was proven by Martin (Conform. Geom. Dyn. 1:24?C27, 1997). Moreover, we construct uniformly quasiregular mappings on $\bar{ {\mathbb{H}}}^{1}$ with large-dimensional branch sets. We prove that for any uniformly quasiregular map g on $\bar{ {\mathbb{H}}}^{1}$ there exists a measurable CR structure ?? which is equivariant under the semigroup ?? generated by g. This is equivalent to the existence of an equivariant horizontal conformal structure.     

Functional Inequalities and Hamilton–Jacobi Equations in Geodesic Spaces

We study the connection between the p-Talagrand inequality and the q-logarithmic Sololev inequality for conjugate exponents p ≥ 2, q ≤ 2 in proper geodesic metric spaces. By means of a general Hamilton–Jacobi semigroup we prove that these are equivalent, and moreover equivalent to the hypercontractivity of the Hamilton–Jacobi semigroup. Our results generalize those of Lott and Villani. They can be applied to deduce the p-Talagrand inequality in the sub-Riemannian setting of the Heisenberg group.     

A High-Throughput Clinical Laboratory Methodology for the Therapeutic Monitoring of Ibrutinib and Dihydrodiol Ibrutinib

Ibrutinib (IBR) is an oral anticancer medication that inhibits Bruton tyrosine kinase irreversibly. Due to the high risk of adverse effects and its pharmacokinetic variability, the safe and effective use of IBR is expected to be facilitated by precision dosing. Delivering suitable clinical laboratory information on IBR is a prerequisite of constructing fit-for-purpose population and individual pharmacokinetic models. The validation of a dedicated high-throughput method using liquid chromatography–mass spectrometry is presented for the simultaneous analysis of IBR and its pharmacologically active metabolite dihydrodiol ibrutinib (DIB) in human plasma. The 6 h benchtop stability of IBR, DIB, and the active moiety (IBR + DIB) was assessed in whole blood and in plasma to identify any risk of degradation before samples reach the laboratory. In addition, four regression algorithms were tested to determine the optimal assay error equations of IBR, DIB, and the active moiety, which are essential for the correct estimation of the error of their future nonparametric pharmacokinetic models. The noncompartmental pharmacokinetic properties of IBR and the active moiety were evaluated in three patients diagnosed with chronic lymphocytic leukemia to provide a proof of concept. The presented methodology allows clinical laboratories to efficiently support pharmacokinetics-based precision pharmacotherapy with IBR.