Application of DTA/DSC and dilatometry for optimization of Ba–Ce–Y–P–Si–O glass phase for composite protonic conductors based on BaCe<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3−<Emphasis Type="Italic">δ</Emphasis></Subscript>

The aim of this work was to determine the influence of chemical composition on thermal and electrical properties of selected glass from the BaO–CeO₂–Y₂O₃–P₂O₅–SiO₂ system. Properties of the investigated glasses were optimized in terms of glass-BaCe_0.9Y_0.1O₃ composite protonic conductor preparation. Three types of glasses with different P₂O₅/SiO₂ ratio were prepared and investigated. The DSC and XRD measurements indicated limited tendency to crystallization of obtained glasses up to T = 1023 K. The dilatometry measurements led to determination of the thermal expansion coefficients (TEC) and the softening point. It was found that obtained glasses soften in temperature range of 903–923 K, depending on the composition which is advantageous from the viewpoint of further preparation and formation of the composite material. The Electrochemical Impedance Spectroscopy measurements done as a function of temperature and gas atmosphere allowed to determine the activation energy of the electrical conductivity. Observed fluctuations of the activation energy with gas atmosphere suggest the possible role of the protonic defects in total conductivity. Based on the obtained results it can be stated that proposed glass system may be considered as the modifying phase for improvement of BaCe_0.9Y_0.1O₃-based materials.     

An ion-imprinted thiocyanato-functionalized mesoporous silica for preconcentration of gold(III) prior to its quantitation by slurry sampling graphite furnace AAS

A gold(III)-imprinted thiocyanato-functionalized silica network of type SBA-15 was prepared by co-condensation of tetraethoxysilane (TEOS) with thiocyanatopropyltriethoxysilane (TCTES) in the presence of Pluronic123 and Au(III) ions. Compared to the non-imprinted material, the imprint has a higher selectivity and adsorption capacity for Au(III). The maximum static adsorption capacity for Au(III) is 475 mg·g^?1 for the ion-imprinted, and 62 mg·g^?1 for the non-imprinted sorbent. The imprint was applied to the sorption of Au(III) from digested geological samples prior to its determination by graphite furnace atomic absorption spectrometry. Adsorption is fast and does not substantially prolong the analytical procedure. Under optimum conditions, the detection limit for Au(III) is 2 ng·g^?1. The method was validated by analyzing certified reference materials, and results were in good agreement with certified values. The procedure was successfully applied to the separation and determination of gold in complex geological samples.

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Graphical abstract Schematic presentation of the preparation of ion-imprinted thiocyanato-functionalized mesoporous silica and its application for the preconcentration of gold from digested soils before its determination by slurry sampling graphite furnace atomic absorption spectrometry (GF AAS).

     

The abundances of fragment ions formed via skeletal rearrangements from 2,5-disubstituted-1,3,4-oxadiazoles and their theoretical calculated stabilities

Protonated molecules of 2,5-di-R1,R2-substituted-1,3,4-oxadiazoles lose isocyanic acid (loss of mass 43) via skeletal rearrangement. This was observed in low-energy CID mass spectra recorded by using electrospray ionisation (ESI). On electron ionisation induced decomposition these compounds also reveal complex skeletal rearrangement, consisting on N2 and CO elimination, leading to the formation of fluorene or indene type ions. It was found that abundances of fragment ions formed in these processes are in good agreement with their theoretically calculated stabilities. In the case of ESI use the fragment ion abundances were calculated in relation to [M+H]+ ion abundances and for EI use, where extensive fragmentations proceed, the sums of the abundances of [M-N2-CO]+. ions and abundances of fragment ions derived from them, were expressed as a percentage of total-ion current.     

The comparative molecular surface analysis (CoMSA) with modified uniformative variable elimination-PLS (UVE-PLS) method: application to the steroids binding the aromatase enzyme

The application of the CoMSA method to analyze 3D QSAR of 50 steroid aromatase inhibitors is described. The 3D QSAR model obtained, reaching a value of cross-validated q(2) = 0.96 (s = 0.31), significantly outperforms those reported in the literature for the CoMFA or CoSA (CoSASA). It is shown that the Uniformative Variable Elimination UVE-PLS or modified iterative UVE procedure (IVE-PLS) can be used for indicating the regions contributing to the binding activity. Thus, after separating the series into two groups of the training and test molecules quite correct external predictions result from the processing of the training set. We proved that the procedure of the data elimination provides stable results, if tested in 50 random runs of the IVE-PLS-CoMSA with different training/test sets. Depending upon the procedure used the quality of the predictions for 25 test molecules is given by SDEP = sum(y(pred)-y(obs))(2)/n)(1/2) = 0.321 - 0.782.     

Sustainable Processes Employing Ionic Liquids for Secondary Alcohols Separation

Summary. Secondary chiral alcohols are very attractive intermediates in organic synthesis of pharmaceutical and the fine-chemical industries. The processes employing ionic liquids to obtain enantiomers of secondary alcohols have become sustainable. Furthermore, physico-chemical properties of ionic liquids opened new possibilities to design “solvent free” processes for the resolution of racemic secondary alcohols. This review is aimed to highlight some of the most important achievements in resolution of secondary alcohols.     

Convergence properties of dynamic string-averaging projection methods in the presence of perturbations

Assuming that the absence of perturbations guarantees weak or strong convergence to a common fixed point, we study the behavior of perturbed products of an infinite family of nonexpansive operators. Our main result indicates that the convergence rate of unperturbed products is essentially preserved in the presence of perturbations. This, in particular, applies to the linear convergence rate of dynamic string-averaging projection methods, which we establish here as well. Moreover, we show how this result can be applied to the superiorization methodology.     

Adducts of rhodium(II) tetraacylates with methionine and its derivatives: 1H and 13C nuclear magnetic resonance spectroscopy and chiral recognition

Complexation of rhodium(II) dimeric tetraacylates: tetraacetate Rh₂AcO₄, tetratrifluoroacetate Rh₂TFA₄ , and (S)-Mosher’s acid salt Rh₂MTPA₄ with both enantiomerically pure and racemic methionine and its derivatives: hydrochloric salt of methionine, hydrochloric salt of methionine methyl ester, N-formyl methionine, N-phthaloyl methionine, N-phthaloyl methyl ester of methionine, and methyl ester of N,N-dimethylmethionine has been investigated by means of ¹H and ¹³C nuclear magnetic resonance (¹H and ¹³C NMR) and absorption electronic spectroscopy in the visible range. Complexation processes were investigated in D₂O or CDCl₃ solutions, depending on the ligands’ and rhodium salts’ solubilities. Some supporting measurements were performed in the solid phase, using ¹³C and ¹⁵N CPMAS NMR techniques.All ligands investigated form 1:1 and 1:2 adducts in the solution, depending on the rhodium salt to ligand molar ratios. The complexation site in the ligands (S atom) was deduced on the basis of the NMR parameter adduct formation shift (Δδ = δ_adduct ? δ_ligand) and calculated chemical shifts (DFT, NMR GIAO). In the cases of the Rh₂TFA₄ and Rh₂MTPA₄ adducts, decreasing the temperature within the range 220–254 K slowed down the ligand exchange and allowed us to observe the signals of all diastereoisomers in the ¹H and ¹³C NMR spectra.