Validation of a fully automated high throughput liquid chromatographic/tandem mass spectrometric method for roxithromycin quantification in human plasma. Application to a bioequivalence study

A fully automated high-throughput liquid chromatography/tandem mass spectrometry (LC-MS/MS) method was developed for the determination of roxithromycin in human plasma. The plasma samples were treated by liquid-liquid extraction (LLE) in 2.2 mL 96-deep-well plates. Roxithromycin and the internal standard clarithromycin were extracted from 100 microL of human plasma by LLE, using methyl t-butyl ether as the organic solvent. All liquid transfer steps were performed automatically using robotic liquid handling workstations. After vortexing, centrifugation and freezing, the supernatant organic solvent was evaporated and reconstituted. Sample analysis was performed by reversed-phase LC-MS/MS, with positive ion electrospray ionization, using multiple-reaction monitoring. The method had a very short chromatographic run time of 1.6 min. The calibration curve was linear for the range of concentrations 50.0-20.0x10(3) ng mL(-1). The proposed method was fully validated and it was proven to be selective, accurate, precise, reproducible and suitable for the determination of roxithromycin in human plasma. Therefore, it was applied to the rapid and reliable determination of roxithromycin in a bioequivalence study after per os administration of 300 mg tablet formulations of roxithromycin.     

Polyhalite and its analogous triple salts

Polyhalite (K₂SO₄ · MgSO₄ · 2CaSO₄ · 2H₂O) and analogue triple salts, where Mg²⁺ is substituted by Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺, have been synthesized. The salts were characterized by thermal analysis, Raman spectroscopy and X-ray powder diffraction. Diffraction patterns and Raman spectra resemble those of natural polyhalite, except K₂SO₄ · CuSO₄ · 2CaSO₄ · 2H₂O. The latter corresponds to the mineral leightonite, which is structurally different. For polyhalite analogues the cell parameters of the triclinic unit cell have been determined from the powder diffraction patterns. The length of the unit cell vectors varies regularly with the ionic radius of the substituted ion M ²⁺ and is explained by changes in the extension of the coordination octahedron of M ²⁺. Thereby increasing distances of the coordinated water molecules at M ²⁺ parallel with decreasing dehydration temperatures of the corresponding polyhalite. Correspondence: Daniela Freyer, Institut für Anorganische Chemie, TU Bergakademie Freiberg, 09599 Freiberg, Germany.     

Development of an Electrochemical Biosensor for the Rapid Detection of Carbofuran Based on Air Stable Lipid Films with Incorporated Calix[4]arene Phosphoryl Receptor

This work describes the preparation of a selective receptor for the rapid, selective and sensitive electrochemical flow injection analysis of carbofuran in foods using air stable lipid films supported on a methacrylate polymer on a glass fiber filter with incorporated artificial receptor. The selective receptor was synthesized by transformation of the ? OH groups of resorcin[4]arene receptor into phosphoryl groups. These lipid films were supported on a methylacrylate polymer (i.e., methacrylic acid was the functional monomer for the polymerization, ethylene glycol dimethacrylate was used as the crosslinker and 2,2′‐azobis‐2‐methylpropionitrile as an initiator). A minisensor device was constructed for the electrochemical flow injection analysis of toxicants based on air stabilized lipid films supported on a polymer. The device can sense the analyte in a drop (50 μL) of sample. Carbofuran was injected into flowing streams of a carrier electrolyte solution. A host‐guest complex formation between the calix[4]arene phosphoryl receptor and carbofuran takes place through hydrogen bonding. This enhances the preconcentration of carbofuran at the lipid membrane surface which in turn causes dynamic alterations of the electrostatic fields and phase structure of membranes; as a result ion current transients were obtained and the magnitude of these signals was correlated to the substrate concentration. The response times were ca. 80 s and carbofuran was determined at concentration levels of nM. The effect of potent interferences included a wide range of compounds and other insecticides. The effect of interference of proteins and lipids was also examined. The reproducibility of the method was checked by recovery experiments in fruit and vegetable samples with satisfactory results.     

Synthesis of 2D Germanane (GeH): a New,Fast, and Facile Approach

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe₂ layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (E_g) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells.     

Reversed phase StrataTM-X resin as sorbent for automatic on-line solid phase extraction atomic absorption spectrometric determination of trace metals: comparison of polymeric-based sorbent materials

A novel on-line flow injection solid phase extraction method for the preconcentration of trace toxic metals prior determination by flame atomic absorption spectrometry (FI-SPE-FAAS) was developed. The potential application of the hydrophobic reversed phase co-polymer sorbent Strata^TM-X packed into an on-line microcolumn for the quantification of Cd(II), Pb(II), Cu(II) and Cr(VI) was demonstrated for the first time. The method was based on the on-line formation of metal complexes using sodium diethyl-dithiocarbamate (DDTC) and on the subsequent retention of them onto the sorbent material. The target analytes were completely eluted by methanol and, subsequently, directed to FAAS for quantification. All chemical and flow variables affecting the performance of the developed method were thoroughly studied and optimised. For a preconcentration time of 90 s and a sampling frequency of 28 h^?1, enhancement factors of 72, 140, 185, 63 and detection limits of 0.18, 1.6, 0.20 and 1.2 μg L ^?1 were obtained for Cd(II), Pb(II), Cu(II) and Cr(VI), respectively. The accuracy of the FI-SPE-FAAS method was evaluated by analysing certified reference materials as well as spiked environmental water samples. Furthermore, a comparative study of the analytical characteristics, the properties as well as the chemical structures of commercial polymeric based sorbent materials was employed. Strata-X sorbent was compared against Hypersep^TM SCX, Bond Elut® Plexa^TM PCX, Oasis-HLB^TM and Nobias^TM PA-1, regarding the adaptation in on-line FI-SPE-FAAS systems for metal determination, and herein presented.     

Dimensions of irreducible modules for partition algebras and tensor power multiplicities for symmetric and alternating groups

The partition algebra \(\mathsf {P}_k(n)\) and the symmetric group \(\mathsf {S}_n\) are in Schur–Weyl duality on the k-fold tensor power \(\mathsf {M}_n^{\otimes k}\) of the permutation module \(\mathsf {M}_n\) of \(\mathsf {S}_n\), so there is a surjection \(\mathsf {P}_k(n) \rightarrow \mathsf {Z}_k(n) := \mathsf {End}_{\mathsf {S}_n}(\mathsf {M}_n^{\otimes k})\), which is an isomorphism when \(n \ge 2k\). We prove a dimension formula for the irreducible modules of the centralizer algebra \(\mathsf {Z}_k(n)\) in terms of Stirling numbers of the second kind. Via Schur–Weyl duality, these dimensions equal the multiplicities of the irreducible \(\mathsf {S}_n\)-modules in \(\mathsf {M}_n^{\otimes k}\). Our dimension expressions hold for any \(n \ge 1\) and \(k\ge 0\). Our methods are based on an analog of Frobenius reciprocity that we show holds for the centralizer algebras of arbitrary finite groups and their subgroups acting on a finite-dimensional module. This enables us to generalize the above result to various analogs of the partition algebra including the centralizer algebra for the alternating group acting on \(\mathsf {M}_n^{\otimes k}\) and the quasi-partition algebra corresponding to tensor powers of the reflection representation of \(\mathsf {S}_n\).     

Stability, thermal homolysis and intermediate phases of solid hydroazafullerene C59HN

Density functional (DFT) calculations, high-temperature electron paramagnetic resonance (EPR) and transmission electron microscopy (TEM) results suggest that thermal homolysis of C59HN involves a remarkably stable intermediate C59N-C59HN* structure characterised by charge redistribution from a C59N* radical to a bonded C59HN.     

Coordination Complexes of a Neutral 1,2,4‐Benzotriazinyl Radical Ligand: Synthesis,Molecular and Electronic Structures,and Magnetic Properties

A series of d‐block metal complexes of the recently reported coordinating neutral radical ligand 1‐phenyl‐3‐(pyrid‐2‐yl)‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl ( 1 ) was synthesized. The investigated systems contain the benzotriazinyl radical 1 coordinated to a divalent metal cation, Mn^II, Fe^II, Co^II, or Ni^II, with 1,1,1,5,5,5‐hexafluoroacetylacetonato (hfac) as the auxiliary ligand of choice. The synthesized complexes were fully characterized by single‐crystal X‐ray diffraction, magnetic susceptibility measurements, and electronic structure calculations. The complexes [Mn( 1 )(hfac)₂] and [Fe( 1 )(hfac)₂] displayed antiferromagnetic coupling between the unpaired electrons of the ligand and the metal cation, whereas the interaction was found to be ferromagnetic in the analogous Ni^II complex [Ni( 1 )(hfac)₂]. The magnetic properties of the complex [Co( 1 )(hfac)₂] were difficult to interpret owing to significant spin–orbit coupling inherent to octahedral high‐spin Co^II metal ion. As a whole, the reported data clearly demonstrated the favorable coordinating properties of the radical 1 , which, together with its stability and structural tunability, make it an excellent new building block for establishing more complex metal–radical architectures with interesting magnetic properties.     

Theoretical study of nonlinear optical properties of cobalt bis (dicarbollide) derivatives: the effect of substituents

In the present work, molecular first-order hyperpolarizability (\(\beta _{\mathrm{tot}}\)) and dipole moment (d) are obtained at B3LYP/6–31G(d,p) level of theory by coupled perturbed Hartree–Fock method within the static approach. The investigated molecules are a series of substituted cobalt bis (dicarbollide) derivatives: Hydrogens bonded to the two carbon atoms are replaced by acceptor and donor electron substituents. Correlations between the Hammett electronic parameters of the substituents and the molecular properties are tested. Among them, the named push–pull compounds produced the largest calculated values of \(\beta _{\mathrm{tot}}\) and d. The UV–Vis spectra are reported for all studied compounds.     

An agent-based model for the bibliometric h-index

We model a virtual scientific community in which authors publish and cite articles. Citations are attributed according to a preferential attachment mechanism. From the numerical simulations, the h-index can be computed. This bottom-up approach reproduces well real bibliometric data. We consider two versions of our model. (1) The single-scientist is controlled by two parameters which can be tuned to reproduce the value of the h-index of many real scientists. Moreover, this model shows how the h-index grows with the number of citations, for a fixed number of articles. We also define an average h-index that can be used to compare the scientific productivity of institutions of different sizes. (2) The multi-scientist model considers a population of scientists and allows us to study the impact of removing citations from the low h-index researchers on the community. Simulations on real bibilometric data, as well as the predictions of the model, show that the h-index eco-system can be strongly affected by such a filtering.