Accurate detection of perchlorate in epoxy resins via chlorine-35 quantitative quadrupolar NMR (qQNMR).

A qQNMR methodology using chlorine-35 as the employed quadrupolar nucleus has been introduced for the first time as a robust and validated method to determine and quantify perchlorate in epoxy resins. The quantification has been carried out by using a calibration curve of lithium perchlorate. The method was validated at seven concentration levels in the range of 0.16 to 2.0 mg mL-1 (1.6 to 20 mM in perchlorate), affording intra- and inter-day accuracies lower than 0.66% (expressed in CV), robustness towards pH, temperature, resin concentration and recycle delay, a limit of detection (LOD) of 0.08 mg mL-1 (0.8 mM in perchlorate), a limit of quantification (LOQ) of 0.16 mg mL-1 (1.6 mM in perchlorate) and probably most important in such applications, having no matrix effect. The method was applied on epoxy resins containing three different types of perchlorate precursors (lithium, potassium and tetramethylammonium), affording excellent quantifications with relative errors below 2.3% compared to the spiked concentrations.

Quantitative Quadrupolar NMR (qQNMR) via nitrogen-14 for the accurate control of L-carnitine in food supplements.

A qQNMR methodology using nitrogen-14 as the quadrupolar nucleus of choice has been introduced for the first time as a robust and validated method to determine and quantify L-carnitine in food supplements. The quantification has been carried out by the alternative use of a calibration curve or by addition of ammonium chloride as internal standard. The method was validated at seven concentration levels in the range of 5.58-99.26 mM, affording intra- and inter day accuracies lower than 6.84% (expressed in CV), robustness towards temperature and recycle delay, limit of detection (LOD) of 2.48 mM, limit of quantification (LOQ) of 5.58 mM and remarkably with absence of matrix effect.

Quantitative quadrupolar NMR (qQNMR) using nitrogen-14 for the determination of choline in complex matrixes.

NMR offers the unique potential to selectively excite the chosen nuclei avoiding in an extraordinary way the matrix effect. Quantitative Nitrogen-14 NMR (14N qNMR) spectroscopy has been introduced for the first time as a robust and validated method to determine choline in a variety of matrixes including quinoa grains, instant coffee and food supplements. A study about the ion pairing of choline bitartrate in aqueous solution by means of diffusion PGSE, NOESY and HOESY NMR have been also provided. Validation of the method within eight concentrations levels (from 1.58 to 79.0 mM) afforded a limit of detection of 400 µg/mL (1.58 mM), a quantification limit of 1000 µg/mL (3.95 mM), excellent linearity (R2 higher than 0.999), intra-/inter-day precisions lower than 1.24% (CV), recoveries of 93.5%-102.5%, and complete absence of matrix effect. The fast and reliable quantification of choline together with the accuracy and simplicity of this new approach make it useful in the development of analytical procedures that could dramatically affect traditional analysis.

Designing Single-Molecule Magnets as Drugs with Dual Anti-Inflammatory and Anti-Diabetic Effects.

We have designed and synthesized two novel cobalt coordination compounds using bumetanide (bum) and indomethacin (ind) therapeutic agents. The anti-inflammatory effects of cobalt metal complexes with ind and bum were assayed in lipopolysaccharide stimulated RAW 264.7 macrophages by inhibition of nitric oxide production. Firstly, we determined the cytotoxicity and the anti-inflammatory potential of the cobalt compounds and ind and bum ligands in RAW 264.7 cells. Indomethacin-based metal complex was able to inhibit the NO production up to 35% in a concentration-dependent manner without showing cytotoxicity, showing around 6-37 times more effective than indomethacin. Cell cycle analysis showed that the inhibition of NO production was accompanied by a reversion of the differentiation processes in LPS-stimulated RAW 264.7 cells, due to a decreased of cell percentage in G0/G1 phase, with the corresponding increase in the number of cells in S phase. These two materials have mononuclear structures and show slow relaxation of magnetization. Moreover, both compounds show anti-diabetic activity with low in vitro cell toxicities. The formation of metal complexes with bioactive ligands is a new and promising strategy to find new compounds with high and enhanced biochemical properties and promises to be a field of great interest.

Design and synthesis of a family of 1D-lanthanide-coordination polymers showing luminescence and slow relaxation of the magnetization.

We have designed and synthesized eight isostructural 1D coordination polymers (CPs) with the general formula {[Ln(aapc)3(DMF)]}n [where Ln(iii) = Y (2), La (3), Nd (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9); and aapc = 3-((anthraquinone-1-yl)amino)propanoate]. These CPs consist of Ln-carboxylate infinite rods in which the bulky anthraquinone scaffolds arise from it in such a way that the resulting supramolecular packing exhibits isolated 1D chains. Solution structures have been corroborated through NMR methods including PGSE and EXSY NMR studies and, due to the presence of lanthanide ions, magnetic and luminescence properties have been studied. Alternating current magnetic measurements of compound 8 show slow relaxation of the magnetization, a characteristic of single molecule magnets (SMMs). The evaluation of solid-state photophysical properties reveals that the aapc scaffold sensitizes lanthanide(iii) based emission of compounds 4-9 both in the visible and near-infrared (NIR) regions at 10 K.

Unprecedented Spectroscopic and Computational Evidence for Allenyl and Propargyl Titanocene(IV) Complexes: Electrophilic Quenching of Their Metallotropic Equilibrium.

The synthesis and structural characterization of allenyl titanocene(IV) [TiClCp2 (CH=C=CH2 )] 3 and propargyl titanocene(IV) [TiClCp2 (CH2 -C≡C-(CH2 )4 CH3 )] 9 have been described for the first time. Advanced NMR methods including diffusion NMR methods (diffusion pulsed field gradient stimulated spin echo (PFG-STE) and DOSY) have been applied and established that these organometallics are monomers in THF solution with hydrodynamic radii (from the Stokes-Einstein equation) of 3.5 and 4.1 Šfor 3 and 9, respectively. Full (1) H, (13) C, Δ(1) H, and Δ(13) C NMR data are given, and through the analysis of the Ramsey equation, the first electronic insights into these derivatives are provided. In solution, they are involved in their respective metallotropic allenyl-propargyl equilibria that, after quenching experiments with aromatic and aliphatic aldehydes, ketones, and protonating agents, always give the propargyl products P (when carbonyls are employed), or allenyl products A (when a proton source is added) as the major isomers. In all the cases assayed, the ratio of products suggests that the metallotropic equilibrium should be faster than the reactions of 3 and 9 with electrophiles. Indeed, DFT calculations predict lower Gibbs energy barriers for the metallotropic equilibrium, thus confirming dynamic kinetic resolution.