Personalized Metabolic Profile by Synergic Use of NMR and HRMS

A new strategy that takes advantage of the synergism between NMR and UHPLC–HRMS yields accurate concentrations of a high number of compounds in biofluids to delineate a personalized metabolic profile (SYNHMET). Metabolite identification and quantification by this method result in a higher accuracy compared to the use of the two techniques separately, even in urine, one of the most challenging biofluids to characterize due to its complexity and variability. We quantified a total of 165 metabolites in the urine of healthy subjects, patients with chronic cystitis, and patients with bladder cancer, with a minimum number of missing values. This result was achieved without the use of analytical standards and calibration curves. A patient’s personalized profile can be mapped out from the final dataset’s concentrations by comparing them with known normal ranges. This detailed picture has potential applications in clinical practice to monitor a patient’s health status and disease progression.     

The h-SbxWO3+2x Oxygen Excess Antimony Tungsten Bronze

We describe the previously unreported oxygen excess hexagonal antimony tungsten bronze with composition Sb_0.5W₃O₁₀, in the following denoted as h-Sb_xWO_3+2x with x=0.167, to demonstrate its analogy to classical A_xWO₃ tungsten bronzes. This compound forms in a relatively narrow temperature range between 580 °C<T<620 °C. It was obtained as a dark-blue polycrystalline powder, and as thin, needle-shaped, blue single crystals. h-Sb_xWO_3+2x crystallizes in the hexagonal space group P6/mmm with the cell parameters a=7.4369(4) Å and c=3.7800(2) Å. The antimony and excess oxygen occupy the hexagonal channels within the network of corner-sharing WO₆ octahedra. h-Sb_xWO_3+2x has a resistivity of ρ_{300 K}≈1.28 mΩ cm at room temperature, with little if any temperature-dependence on cooling. DFT calculations on a simplified model for this compound find a metallic-like electronic structure with the Fermi level falling within rather flat bands, especially around the Γ point.     

Interaction of mixed-donor macrocycles containing the 1,10-phenanthroline subunit with selected transition and post-transition metal ions: metal ion recognition in competitive liquid-liquid solvent extraction of Cu(II), Zn(II), Pb(II), Cd(II), Ag(I), and Hg(II)

Two new mixed aza-thia crowns 5-aza-2,8-dithia[9]-(2,9)-1,10-phenanthrolinophane (L(4)) and 2,8-diaza-5-thia[9]-(2,9)-1,10-phenanthrolinophane (L(7)) have been synthesized and characterized. The coordination behavior of L(4) and L(7) toward the metal ions Cu(II), Zn(II), Pb(II), Cd(II), Hg(II), and Ag(I) was studied in aqueous solution by potentiometric methods, in CD3CN/D2O 4:1 (v/v) by (1)H NMR titrations and in the solid state. The data obtained were compared with those available for the coordination behavior toward the same metal ions of structurally analogous mixed donor macrocyclic ligands L(1)-L(3), L(5), L(6): all these contain a phenanthroline subunit but have only S/O/N(aromatic) donor groups in the remaining portion of the ring and are, therefore, less water-soluble than L(4) and L(7). The complexes [Cd(NO3)2(L(5))], [Pb(L(7))](ClO4)2 x 1/2MeCN, [Pb(L(4))](ClO4)2 x MeCN, and [Cu(L(7))](ClO4)2 x 3/2MeNO2 were characterized by X-ray crystallography. The efficacy of L(1)-L(7) in competitive liquid-liquid metal ion extraction of Cu(II), Zn(II), Cd(II), Pb(II), Ag(I), and Hg(II) was assessed. In the absence of Hg(II), a clear extraction selectivity for Ag(I) was observed in all systems investigated.     

Use of Lanthanide‐Containing Polyoxometalates to Sensitise the Emission of Fluorescent Labelled Serum Albumin

Monitoring the interaction of biomolecules is important, and the use of energy transfer is a principal technique in elucidating nanoscale interactions. Lanthanide compounds are promising luminescent probes for biological samples as their emission is longer‐lived than any native autofluorescence. Polyoxometalates (POMs) are interesting structural motifs to incorporate lanthanides, offering low toxicity and a size pertinent for biological applications. Here, we employ iso‐structured POMs containing either terbium or europium and assess their interaction with serum albumin by sensitisation of a fluorescent tag on the protein via LRET (luminescence resonance energy transfer) by exciting the lanthanide. Time‐resolved measurements showed energy transfer with an efficiency of over 90 % for the POM–protein systems. The Tb–POM results were relatively straightforward, while those with the iso‐structured Eu–POM were complicated by the effect of protein shielding from the aqueous environment.     

Synthesis and characterization of novel fluorinated poly(oxomolybdates)

Two novel poly(oxofluoromolybdate) clusters, [Mo6O18F6]6- and [Mo7O22F3]5-, have emerged from systematic field studies on the hydrothermal fluorination of poly(oxometalates). They are accessible via the hydrothermal treatment of Mo(VI)-based precursors in the presence of MF additives (M = Li, Na, Cs, NMe4). The new fluorinated polyanions are stabilized by specific alkali-cation combinations, and their packing motifs can be tuned through the careful choice of cations and synthetic parameters. The [Mo6O18F6]6- anion can be described as a cored and fluorinated form of the Anderson-Evans cluster type. It is stabilized by the interaction of two alkali cations with the fluorinated faces of the ring-shaped anion. The partial replacement of these capping alkali cations by the bulky, organic NMe4(+) cation leads to the formation of [Mo7O22F3](5-)-based compounds. Thus, the extent of fluorination can be controlled through the polarizability of the cationic environment: in the [Mo7O22F3]5- anion, half of the fluoride atoms of the [Mo6O18F6]6- anion are replaced by a capping MoO4 tetrahedron, thereby rendering this anion a fluorinated, lacunar derivative of the alpha-[Mo8O26]4- octamolybdate anion. All compounds have been structurally characterized by single-crystal X-ray diffraction and solid-state NMR spectroscopy. The templating role of the alkali cations is discussed and explained with the help of electrostatic calculations.     

Efficiency of the medical care industry: Evidence from the Italian regional system

What might be the relation between clinical research and efficiency of medical care suppliers? Is the hypothesis of a positive relation consistent? Considering efficiency as the supplier’s ability to maximize the number of patients hospitalized in a mobility process among regions (i.e. mobility balance), this work aims at highlighting the existence of a positive externality of pharmaceutical clinical research on that kind of efficiency. In other words, an externality is able to affect the patients’ perception of good/bad quality of outputs supplied by the medical care industry, leading their mobility process. Taking Italy and the mobility of patients among regions into account, an Operational Research study will be performed in order to support this assumption.The goal of this work is to show an alternative way to increase the efficiency of medical care suppliers on the market of health care, that is to say, through their competitiveness on the market of human experimentation.