Rapid determination of 226Ra in drinking water samples using dispersive liquid-liquid microextraction coupled with liquid scintillation counting

A new radioanalytical method was developed for rapid determination of ²²⁶Ra in drinking water samples. The method is based on extraction and preconcentration of ²²⁶Ra from a water sample to an organic solvent using a dispersive liquid-liquid microextraction (DLLME) technique followed by radiometric measurement using liquid scintillation counting. In DLLME for ²²⁶Ra, a mixture of an organic extractant (toluene doped with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone) and a disperser solvent (acetonitrile) is rapidly injected into the water sample resulting in the formation of an emulsion. Within the emulsion, ²²⁶Ra reacts with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone and partitions into the fine droplets of toluene. The water/toluene phases were separated by addition of acetonitrile as a de-emulsifier solvent. The toluene phase containing ²²⁶Ra was then measured by liquid scintillation counting. Several parameters were studied to optimize the extraction efficiency of ²²⁶Ra, including water immiscible organic solvent, disperser and de-emulsifier solvent type and their volume, chelating ligands for ²²⁶Ra and their concentrations, inorganic salt additive and its concentration, and equilibrium pH. With the optimized DLLME conditions, the accuracy (expressed as relative bias, B _r ) and method repeatability (expressed as relative precision, S _B ) were determined by spiking ²²⁶Ra at the maximum acceptable concentration level (0.5 Bq L⁻¹) according to the Guidelines for Canadian Drinking Water Quality. Accuracy and repeatability were found to be less than −5% (B _r ) and less than 6% (S _B ), respectively, for both tap water and bottled natural spring water samples. The minimum detectable activity and sample turnaround time for determination of ²²⁶Ra was 33 mBq L⁻¹ and less than 3 h, respectively. The DLLME technique is selective for extraction of ²²⁶Ra from its decay progenies.     

Composition dependent phase transformation of Pt0.5−x Mn0.5+x from A1 to L10 phase

Pt_0.5−x Mn_0.5+x films were prepared by sputtering deposition of Pt foil and Mn target to study the order-disorder transition from a thermodynamic metastable fcc (A1) phase to L1₀ phase. Both Differential Scanning Calorimetry and High Temperature X-Ray Diffraction studies showed the phase transformation from fcc to the L1₀ structure for the Pt_0.50Mn_0.50 and Pt_0.40Mn_0.60 samples but along completely different kinetic paths. A composition dependent phase transformation was observed by comprehensive Differential Scanning Calorimetry studies on a series of Pt_0.5−x Mn_0.5+x samples. The changes of the lattice parameter and the cell volume of L1₀ Pt_0.5−x Mn_0.5+x as a function of composition suggest that the anti-site is not the dominant point defect for L1₀ Pt_0.5−x Mn_0.5+x .     

Liquid analysis dielectric capillary barrier discharge

In this study a simple micro-tube-based system for analysis of metal-containing liquids is introduced and its analytical performance is evaluated. It is based on a miniaturised dielectric barrier discharge driven at atmospheric pressure. The emission lines of various elements are observed. The system is developed for quantitative measurements and the limits of detection are determined. Because of very low flow rates of just μL min⁻¹ the approach requires extremely low sample volumes.     

Light-Sensitive Phenacyl Crosslinked Dextran Hydrogels for Controlled Delivery**

Stimuli-responsive soft materials enable controlled release of loaded drug molecules and biomolecules. Controlled release of potent chemotherapeutic or immunotherapeutic agents is crucial to reduce unwanted side effects. In an effort to develop controlled release strategies that can be triggered by using Cerenkov luminescence, we have developed polymer hydrogels that can release bovine serum albumin and immunoglobulin G by using light (254 nm–375 nm) as a trigger. We describe the synthesis and photochemical characterization of two light sensitive phenacyl bis-azide crosslinkers that are used to prepare transparent self-supporting hydrogel patches. One crosslinker was designed to optimize the overlap with the Cerenkov luminescence emission window, bearing an π-extended phenacyl core, resulting in a high quantum yield (14 %) of photocleavage when irradiated with 375 nm light. We used the extended phenacyl crosslinker for the preparation of protein-loaded dextran hydrogel patches, which showed efficient and selective dosed release of bovine serum albumin or immunoglobulin G after irradiation with 375 nm light. Cerenkov-triggered release is as yet inconclusive due to unexpected side-reactivity. Based on the high quantum yield, efficient release and large overlap with the Cerenkov window, we envision application of these photosensitive soft materials in radiation targeted drug release.     

Pyrimidoquinazolinophenanthroline Opens Next Chapter in Design of Bridging Ligands for Artificial Photosynthesis**

The synthesis and detailed characterization of a new Ru polypyridine complex containing a heteroditopic bridging ligand with previously unexplored metal-metal distances is presented. Due to the twisted geometry of the novel ligand, the resultant division of the ligand in two distinct subunits leads to steady state as well as excited state properties of the corresponding mononuclear Ru(II) polypyridine complex resembling those of prototype [Ru(bpy)₃]²⁺ (bpy=2,2'-bipyridine). The localization of the initially optically excited and the nature of the long-lived excited states on the Ru-facing ligand spheres is evaluated by resonance Raman and fs-TA spectroscopy, respectively, and supported by DFT and TDDFT calculations. Coordination of a second metal (Zn or Rh) to the available bis-pyrimidyl-like coordination sphere strongly influences the frontier orbitals, apparent by, for example, luminescence quenching. Thus, the new bridging ligand motif offers electronic properties, which can be adjusted by the nature of the second metal center. Using the heterodinuclear Ru−Rh complex, visible light-driven reduction of NAD⁺ to NADH was achieved, highlighting the potential of this system for photocatalytic applications.     

In Situ Grignard Metalation Method for the Synthesis of Hauser Bases

The in situ Grignard Metalation Method (iGMM) is a straightforward one-pot procedure to quickly produce multigram amounts of Hauser bases R₂N-MgBr which are valuable and vastly used metalation reagents and novel electrolytes for magnesium batteries. During addition of bromoethane to a suspension of Mg metal and secondary amine at room temperature in an ethereal solvent, a smooth reaction yields R₂N-MgBr under evolution of ethane within a few hours. A Schlenk equilibrium is operative, interconverting the Hauser bases into their solvated homoleptic congeners Mg(NR₂)₂ and MgBr₂ depending on the solvent. Scope and preconditions are studied, and side reactions limiting the yield have been investigated. DOSY NMR experiments and X-ray crystal structures of characteristic examples clarify aggregation in solution and the solid state.     

Between Two Chairs: Combination of Theory and Experiment for the Determination of the Conformational Dynamics of Xylosides

The conformational properties of monosaccharides constitute fundamental features of oligosaccharides. While the energy landscape of monosaccharides can be altered by a specific biochemical environment or by chemical modifications, the analysis of resulting dynamic conformational equilibria is not feasible by experimental means alone. In this work, a series of β-d -xylopyranosides is used to outline how a combination of experimental NMR parameters and computed molecular properties can be used to determine conformers and quantify the composition of conformational equilibria. We demonstrate that identifying the most stable conformers using energy calculations is challenging and computing of NMR shieldings is typically not sensitive enough. On the other hand, computed spin-spin coupling constants for the xyloside ring can be used to unambiguously assign experimental NMR data of dynamic conformational equilibria and quantify the ratio of different conformers in the mixture. As a proof of principle, this procedure allowed to analyze a hitherto unknown dynamic equilibrium of a diamino-xyloside as a precursor of a molecular switch.