Online large volume sample staking preconcentration and separation of enantiomeric GHRH analogs by capillary electrophoresis

A capillary electrophoresis method is proposed to analyze the four most well-known growth hormone–releasing hormone (GHRH) analogs that are misused by athletes. Dimethyl-β-cyclodextrin used as a chiral selector allowed, for the first time, the separation of those basic peptide analogs, including enantiopeptides (sermorelin and CJC-1293) that differ by the chirality of only one amino acid. To increase the method sensitivity, electrokinetic preconcentration methods have been investigated. The large volume sample stacking with polarity switching (PS-LVSS) method with an injected sample volume corresponding to 80% of the capillary one was found superior to the sweeping in terms of signal enhancement factor (SEF). Acid and organic solvent addition to the sample (0.1 mM phosphoric acid with 30% methanol) led to a twofold signal improvement, when compared to water as a matrix. We increased capillary dimensions to provide a signal enhancement through the injection of a larger sample volume. Finally, using a combination of the optimized PS-LVSS preconcentration with the chiral capillary zone electrophoresis (CZE), the GHRH analogs were separated and limits of detection between 75 and 200 ng/mL were reached. This method was successfully applied to urine after a desalting step. An optimized C18 SPE was used for that purpose in order to provide low sample conductivity (<130 µS/cm) and preserve the efficiency of LVSS preconcentration. SEF of 640 was obtained with desalted urine spiked with sermorelin by comparison to the CZE (without preconcentration) method.     

A Convenient Procedure for N-Amination of 4-OXO-1,4-Dihydroquinolines

A high yielding N-amination of quinolones at low temperature via the use of O-mesitylenesulfonylhydroxylamine is reported.     

A perturbation-method-based a posteriori estimator for the planewave discretization of nonlinear Schrödinger equations

In this Note, we propose a new method, based on perturbation theory, to post-process the planewave approximation of the eigenmodes of periodic Schrödinger operators. We then use this post-processing to construct an accurate a posteriori estimator for the approximations of the (nonlinear) Gross–Pitaevskii equation, valid at each step of a self-consistent procedure. This allows us to design an adaptive algorithm for solving the Gross–Pitaevskii equation, which automatically refines the discretization along the convergence of the iterative process, by means of adaptive stopping criteria.     

Polyamine-substituted epoxy-grafted silica for aqueous metal recovery

Glycidoxypropyltriethoxysilane (GPS) was used as a reactive silane to graft metal- complexing ligands onto silica gel in aqueous media under mild conditions. The synthesis entailed the reaction of GPS with silica gel, followed by grafting polyamine onto the epoxy functional group. GPS was added to silica gel in ethanol with 5 vol. % water and the mixture was air-dried for 24 h. Subsequently, excess amounts of polyamines: triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine were individually added to the silanised silica, followed by solvent evaporation and ovendrying at 60°C. The ligand-grafted silica gel particles showed a rapid heavy metal uptake in batch or flow-through experiments with capacities reaching 0.1 mmol g⁻¹ for copper, zinc, cadmium, or lead ions. Columns packed with the modified particles could be readily regenerated by acid-washing with only a small decrease in activity. The particles could be used for the colourimetric detection of heavy metal pollution or for pre-concentration for analytical purposes. Competition between Cu²⁺, Zn²⁺, Pb²⁺, and Cd²⁺ ions for the three synthesised silica showed that Cu²⁺ ions were adsorbed more strongly than the other metal ions. The general method developed can be applied to graft other molecules with terminal amino groups for other purposes.     

Tuning the Reactivity of a Heterogeneous Catalyst using N-Heterocyclic Carbene Ligands for C−H Activation Reactions

We report the dramatic impact of the addition of N-heterocyclic carbenes (NHCs) on the reactivity and selectivity of heterogeneous Ru catalysts in the context of C−H activation reactions. Using a simple and robust method, we prepared a series of new air-stable catalysts starting from commercially available Ru on carbon (Ru/C) and differently substituted NHCs. Associated with C−H deuteration processes, depending on Ru/C-NHC ratios, the chemical outcome can be controlled to a large extent. Indeed, tuning the reactivity of the Ru catalyst with NHC enabled: 1) increased chemoselectivity and the regioselectivity for the deuteration of alcohols in organic media; 2) the synthesis of fragile pharmaceutically relevant deuterated heterocycles (azine, purine) that are otherwise completely reduced using unmodified commercial catalysts; 3) the discovery of a novel reactivity for such heterogeneous Ru catalysts, namely the selective C-1 deuteration of aldehydes.     

Hydrogen Isotope Exchange Catalyzed by Ru Nanocatalysts: Labelling of Complex Molecules Containing N-Heterocycles and Reaction Mechanism Insights

Ruthenium nanocatalysis can provide effective deuteration and tritiation of oxazole, imidazole, triazole and carbazole substructures in complex molecules using D₂ or T₂ gas as isotopic sources. Depending on the substructure considered, this approach does not only represent a significant step forward in practice, with notably higher isotope uptakes, a broader substrate scope and a higher solvent applicability compared to existing procedures, but also the unique way to label important heterocycles using hydrogen isotope exchange. In terms of applications, the high incorporation of deuterium atoms, allows the synthesis of internal standards for LC-MS quantification. Moreover, the efficacy of the catalyst permits, even under subatmospheric pressure of T₂ gas, the preparation of complex radiolabeled drugs owning high molar activities. From a fundamental point of view, a detailed DFT-based mechanistic study identifying undisclosed key intermediates, allowed a deeper understanding of C−H (and N−H) activation processes occurring at the surface of metallic nanoclusters.     

Structural and vibrational properties of Ca2FeH6 and Sr2RuH6

The structural and vibrational properties of the isostructural compounds Ca₂FeH₆ and Sr₂RuH₆ are determined by periodic DFT calculations and compared with their previously published experimental crystal structures as well as new experimental vibrational data. The analysis of the vibrational data is extended to the whole series of alkaline-earth iron and ruthenium hydrides A₂TH₆ (A=Mg, Ca, Sr; T=Fe, Ru) in order to identify correlations between selected frequencies and the T-H bond length. The bulk moduli of Ca₂FeH₆ and Sr₂RuH₆ have also been determined within DFT. Their calculated values prove to compare well with the experimental values reported for Mg₂FeH₆ and several other compounds of this structure.     

Macrocyclic 14-Membered Ring Diketal Dilactams: Evaluation of their Divalent Cation Binding Properties

The binding abilities of a new class of 14-membered ring ligands bearing diketal dilactam functions were explored by UV-visible spectrophotometry. Their formation constants, determined in THF solution, showed appreciable complexation with divalent cations (stability order: Sr²⁺≥Ca²⁺>Zn²⁺≥Mg²⁺>Ba²⁺) whereas no association was observed with monovalent cations. The stoichiometry of the complexes formed was essentially 1:1 although sometimes a low percentage (<10%) of 1:2 (cation–ligand) species was detected. The corresponding formation constants determined by computation (STAR program) were in the range 1.5<log?β ¹¹<4.8 and 4.4<log?β ¹²<7.1. They depend significantly on the nature of the substituents. In addition, solvent extractions carried out in a water–chloroform system showed the highest constants (log K ^ex) for the most substituted macrocycles 7b and 7c (norephedrine series) with a lipophilic skeleton.     

Coherent frequency conversion in a superconducting artificial atom with two internal degrees of freedom

By adding a large inductance in a dc-SQUID phase qubit loop, one decouples the junctions' dynamics and creates a superconducting artificial atom with two internal degrees of freedom. In addition to the usual symmetric plasma mode (s mode) which gives rise to the phase qubit, an antisymmetric mode (a mode) appears. These two modes can be described by two anharmonic oscillators with eigenstates |ns> and |na> for the s and a mode, respectively. We show that a strong nonlinear coupling between the modes leads to a large energy splitting between states |0s,1a> and |2s,0a>. Finally, coherent frequency conversion is observed via free oscillations between the states |0s,1a> and |2s,0a>.