Mechanism of Alkyl Migration in Diorganomagnesium 2,6-Bis(imino)pyridine Complexes: Formation of Grignard-Type Complexes with Square-Planar Mg(II) Centers

Dialkylmagnesium compounds [MgR2L2] (R = n-Bu, L = none or R = Bn, L = THF) react with 2,6-bis(imino)pyridines (BIP) to afford different types of Mg(II) alkyl complexes, depending on the nature of R. For R = n-Bu, thermally stable products resulting from selective alkyl transfer to the pyridine nitrogen (N1) atom are obtained. However, NMR studies showed that the reaction of [Mg(Bn)2THF2] with iPrBIP at −65 °C leads to a thermally unstable product arising from benzyl migration to position C2 in the pyridine ring. Above +5 °C, this compound rearranges, cleanly yielding a mixture of two isomeric complexes, in which the benzyl group has migrated to positions C3 or C4 of the central ring, respectively. Similar isomeric mixtures were obtained when [Mg(Bn)2THF2] was reacted with iPrBIP or MesBIP at room temperature. Such mixtures are thermally stable below 80 °C, but at this temperature, the 3-benzyl isomer converts into the thermodynamically favored 4-benzyl product, albeit not quantitatively. An alternate route was devised for the selective syntheses of the latter type of compounds. The X-ray diffraction structure of one of them provided an unusual example of a square-planar alkylmagnesium(II) center.Ministerio de Economía e Innovación CTQ2015-68978-

In-silico modeling to compare radiofrequency-induced thermal lesions created on myocardium and thigh muscle

[EN] Beating heart (BH) and thigh muscle (TM) are two pre-clinical models aimed at studying the lesion sizes created by radiofrequency (RF) catheters in cardiac ablation. Previous experimental results have shown that thermal lesions created in the TM are slightly bigger than in the BH. Our objective was to use in-silico modeling to elucidate some of the causes of this difference. In-silico RF ablation models were created using the Arrhenius function to estimate lesion size under different energy settings (25 W/20 s, 50 W/6 s and 90 W/4 s) and parallel, 45 degrees and perpendicular catheter positions. The models consisted of homogeneous tissue: myocardium in the BH model and striated muscle in the TM model. The computer results showed that the lesion sizes were generally bigger in the TM model and the differences depended on the energy setting, with hardly any differences at 90 W/4 s but with differences of 1 mm in depth and 1.5 m in width at 25 W/20 s. The higher electrical conductivity of striated muscle (0.446 S/m) than that of the myocardium (0.281 S/m) is possibly one of the causes of the higher percentage of RF energy delivered to the tissue in the TM model, with differences between models of 2-5% at 90 W/4 s, similar to 9% at 50 W/6 s and similar to 10% at 25 W/20 s. Proximity to the air-blood interface (just 2 cm from the tissue surface) artificially created in the TM model to emulate the cardiac cavity had little effect on lesion size. In conclusion, the TM-based experimental model creates fairly similar-sized lesions to the BH model, especially in high-power short-duration ablations (50 W/6 s and 90 W/4 s). Our computer results suggest that the higher electrical conductivity of striated muscle could be one of the causes of the slightly larger lesions in the TM model.This research was funded by the Spanish Ministerio de Ciencia, Innovacion y Universidades/Agencia Estatal de Investigacion MCIN/AEI/10.13039/501100011033 (Grant number: RTI2018-094357-B-C21)Pérez, JJ.; Berjano, E.; González-Suárez, A. (2022). In-silico modeling to compare radiofrequency-induced thermal lesions created on myocardium and thigh muscle. Bioengineering. 9(7):1-13. https://doi.org/10.3390/bioengineering9070329S1139

How far the zone of heat-induced transient block extends beyond the lesion during RF catheter cardiac ablation

This is an Accepted Manuscript of an article published by Taylor & Francis in International Journal of Hyperthermia on 02-01-2023, available online: http://www.tandfonline.com/ https://doi.org/10.1080/02656736.2022.2163310[EN] Purpose While radiofrequency catheter ablation (RFCA) creates a lesion consisting of the tissue points subjected to lethal heating, the sublethal heating (SH) undergone by the surrounding tissue can cause transient electrophysiological block. The size of the zone of heat-induced transient block (HiTB) has not been quantified to date. Our objective was to use computer modeling to provide an initial estimate. Methods and materials We used previous experimental data together with the Arrhenius damage index (omega) to fix the omega values that delineate this zone: a lower limit of 0.1-0.4 and upper limit of 1.0 (lesion boundary). An RFCA computer model was used with different power-duration settings, catheter positions and electrode insertion depths, together with dispersion of the tissue's electrical and thermal characteristics. Results The HiTB zone extends in depth to a minimum and maximum distance of 0.5 mm and 2 mm beyond the lesion limit, respectively, while its maximum width varies with the energy delivered, extending to a minimum of 0.6 mm and a maximum of 2.5 mm beyond the lesion, reaching 3.5 mm when high energy settings are used (25 W-20s, 500 J). The dispersion of the tissue's thermal and electrical characteristics affects the size of the HiTB zone by +/- 0.3 mm in depth and +/- 0.5 mm in maximum width. Conclusions Our results suggest that the size of the zone of heat-induced transient block during RFCA could extend beyond the lesion limit by a maximum of 2 mm in depth and approximately 2.5 mm in width.This work was supported by Spanish Ministerio de Ciencia, Innovacion y Universidades/Agencia Estatal de Investigacion IMCIN/AEI/10.13039/ 501100011033 (Grant RTI2018-094357-B-C21).Pérez, JJ.; Berjano, E.; González Suárez, A. (2023). How far the zone of heat-induced transient block extends beyond the lesion during RF catheter cardiac ablation. International Journal of Hyperthermia. 40(1):1-10. https://doi.org/10.1080/02656736.2022.216331011040

Oxygen-Induced Dimerization of Alkyl-Manganese(II) 2,6-Bisiminopyridine Complexes: Selective Synthesis of a New Ditopic NNN-Pincer Ligand

The outcome of the reaction of manganese(II) dialkyls with 2,6-bisiminopyridine (BIP) ligands is dramatically altered by the presence of very small amounts of oxygen (< 0.5 mol %), leading to binuclear species. These arise from the dimerization of the initial product, a Mn(II) 4-alkyl-2,6-bisiminodihydropyridinate alkyl complex. Cleavage of the binuclear Mn products with methanol affords the free dimeric bases, which can be regarded as a special type of ditopic NNN pincer ligand with an unusual tricyclic framework. The coordinative ability of the new ligands has been probed with the syntheses of Zn and Pd organometallic derivativesMinisterio de Economía e Innovación TQ2015- 68978-

Flow injection determination of total catechins and procyanidins in white and red wines

An easily automatable flow-injection (FI) method for the determination of total catechins is reported. The method is based on the reaction of vanillin in acid medium to yield a coloured product with maximum absorption at 500 nm. After optimisation by the univariate and multivariate approaches as required, the linear range was established (between 10 and 90 mgL-1 and 10 and 250 mgL-1 for white and red wines, respectively). Then, the assessment of the proposed versus the reference method was studied in terms of repeatability (2.57 mgL-1), reproducibility (3.56 mgL-1) (no significant differences were found), detection and quantification limits (not far from those of the reference method and always sufficient for the determination of catechins in any type of wine), traceability (excellent correlation under all conditions) and sample throughput (23 samples h-1 for the proposed method versus 3 samples h-1 for the reference method)

Flow injection determination of readily assimilable nitrogen compounds during vinification

A flow injection method for the determination of readily assimilable nitrogen (r.a.n.), i.e. ammonium and aminated nitrogen, is reported. The difference in pH of the sample in the presence and absence of formaldehyde, which blocks the amino function, provides the value of r.a.n. by monitoring the changes in absorbance of bromothymol blue at 616 nm. The detection and quantification limits are 10 and 11.6 mg l-1, respectively; the reproducibility and repeatability are 3.94 mg l-1 and 1.35 mg l-1, respectively; and the sample throughput is 20 samples h-1. The method has been applied to the analysis of 120 samples of must and wine subjected to biological aging. The proposed method also provides good correlation with the reference method used in routine analysis, and it is faster and gives sufficient precision for wineries requirements

Use of superheated liquids for the extraction of non-volatile compounds from wood: HPLC studies

A study of the extraction of oak wood compounds using superheated water-ethanol mixtures ranging from 10 to 60% ethanol is reported. Identification and characterization of the extracted compounds have been made by high performance liquid chromatography. The extraction has been performed using the static mode by single or repetitive cycles. The variables affecting the extraction process have been studied and their optimum values established (extraction time: 50 min; pressure: 40 atm; extraction temperature: 180º C). The study allows to compare the non-volatile polyphenol fractions obtained in this way with those present in commercial samples with fully agreement between them. In addition, the method allows manipulation of the extract composition by changing the working pressure, temperature and water-ethanol ratio

Assessment of the Sampling Performance of Multiple-Copy Dynamics versus a Unique Trajectory

The goal of the present study was to ascertain the differential performance of a long molecular dynamics trajectory versus several shorter ones starting from different points in the phase space and covering the same sampling time. For this purpose, we selected the 16-mer peptide Bak(16)BH3 as a model for study and carried out several samplings in explicit solvent. These samplings included an 8 mu s trajectory (sampling Si); two 4 us trajectories (sampling S2); four 2 mu s trajectories (sampling S3); eight 1 mu s trajectories (sampling S4); 16 0.5 mu s trajectories (sampling S5), and 80 0.1 mu s trajectories (sampling S6). Moreover, the 8 mu s trajectory was further extended to 16 pis to have reference values of the diverse properties measured. The diverse samplings were compared qualitatively and quantitatively. Among the former, we carried out a comparison of the conformational profiles of the peptide using cluster analysis. Moreover, we also gained insight into the interchange among these structures along the sampling process. Among the latter, we computed the number of new conformational patterns sampled with time using strings defined from the conformations attained by each of the residues in the peptide. We also compared the locations and depths of the obtained minima on the free energy surface using principal component analysis. Finally, we also compared the helical profiles per residue at the end of the sampling process. The results suggest that a few short molecular dynamics trajectories may provide better sampling than one unique trajectory. Moreover, this procedure can also be advantageous to avoid getting trapped in a local minimum. However, caution should be exercised since short trajectories need to be long enough to overcome local barriers surrounding the starting point and the required sampling time depends on the number of degrees of freedom of the system under study. An effective way to gain insight into the minimum MD trajectory length is to monitor the convergence of different structural features, as shown in the present Wor

An analytical representation of the ground potential energy surface (2A') of the H + Cl2 → HCl + Cl and Cl + HCl → HCl + Cl reactions, based on ab initio calculations

In this work we have studied at an ab initio level the lowest 2A′ potential energy surface (PES) of the HCl2 system. This PES is involved in the H(2S)+Cl2(X 1Σ+g)→HCl(X 1Σ+)+Cl(2P) and Cl(2P)+HCl(X 1Σ+)→HCl(X 1Σ+)+Cl(2P) gas phase elementary chemical reactions. The former reaction is an important chemical laser while the second one is the most frequently used prototype of heavy-light-heavy reaction. A large number of points on the 2A′ PES have been calculated at the PUMP2/6-311G(3d2 f,3p2d) ab initio level. The ab initio calculations show the existence of two angular transition states with negligible or very small barriers to collinearity. This and other properties of the PES are in agreement with previous studies. An analytical expression based on a many-body expansion has been used to obtain a satisfactory fit of the 740 ab initio points calculated, with a root-mean-square deviation within the range of the estimated ab initio method error margin. This analytical representation of the 2A′ PES has been used to evaluate the variational transition state theory thermal rate constants of the above-mentioned reactions, including also the Cl+DCl reaction, and quite good agreement has been obtained when comparing with experimental results. The analytical PES obtained in this work is suitable for use in studies on the kinetics and dynamics of the HCl2 system

An ab initio analytical potential energy surface for the O(3P) + CS(X1Σ+) → CO(X1Σ+) + S(3P) reaction useful for kinetic and dynamical studies

The N(4Su) + NO(X 2Π) → N 2(X 1Σg+) + O( 3Pg) reaction plays an important role in the upper atmosphere chemistry and as a calibration system for discharge flow systems. Surprisingly, very little theoretical and experimental work has been devoted to the characterization of the dynamical features of this system. In this work a Sorbie-Murrell expression for the lowest 3A″ potential energy surface (PES) connecting reactants in their ground electronic states based upon the fitting of an accurate ab initio CI grid of points has been derived. The PES fitted shows no barrier to reaction with respect to the reactants asymptote in accordance with experimental findings and becomes highly repulsive as the NNO angle is varied away from the saddle point geometry. The results of preliminary quasiclassical trajectory calculations on this surface reproduce very well the experimental energy disposal in products, even though the vibrational distribution derived from trajectories seems to be a bit cooler than the experimental data. Moreover, thermal rate constants derived from trajectories are in excellent accordance with experimental value