Electrocatalytic properties of platinum nanocenters electrogenerated at ultra-trace levels within zeolitic phosphododecatungstate cesium salt matrices

A unique preparation method of obtaining stable composite film (with ultra-low platinum content) highly active towards oxygen reduction and hydrogen oxidation is presented here. The matrix for platinum centers consists of high-surface-area zeolite-type acidic salt of cesium phosphododecatungstate (Cs_2.5H_0.5PW₁₂O₄₀) admixed with carbon (Vulcan XC-72) carriers. Platinum nanoparticles were deposited on the working electrode modified with matrix via corrosion of platinum counter electrode during cyclic voltammetry experiment conducted in acid electrolyte containing chloride ions. The results obtained from rotating disk voltammetry revealed that the composite film containing Pt nanoparticles at very low loadings (on the level of 2–5 μg cm^?2) demonstrated remarkable electrocatalytic activity towards both oxygen reduction and hydrogen oxidation, particularly, when compared to the performance of the Cs_2.5H_0.5PW₁₂O₄₀-free system (i.e., containing only Vulcan support) prepared and examined under analogous conditions. The phenomenon should be primarily ascribed to the mesoporous nature of the matrix enabling immobilization and stabilization of small catalytic nanoparticles (1–2 nm diameters) inside the pores as well as to high surface acidity of the polyoxometalate-based salt providing proton-rich environment at the electrocatalytic interface.     

Targeted and Untargeted Metabolomic Analyses Reveal Organ Specificity of Specialized Metabolites in the Model Grass Brachypodium distachyon

Brachypodium distachyon, because of its fully sequenced genome, is frequently used as a model grass species. However, its metabolome, which constitutes an indispensable element of complex biological systems, remains poorly characterized. In this study, we conducted comprehensive, liquid chromatography-mass spectrometry (LC-MS)-based metabolomic examination of roots, leaves and spikes of Brachypodium Bd21 and Bd3-1 lines. Our pathway enrichment analysis emphasised the accumulation of specialized metabolites representing the flavonoid biosynthetic pathway in parallel with processes related to nucleotide, sugar and amino acid metabolism. Similarities in metabolite profiles between both lines were relatively high in roots and leaves while spikes showed higher metabolic variance within both accessions. In roots, differences between Bd21 and Bd3-1 lines were manifested primarily in diterpenoid metabolism, while differences within spikes and leaves concerned nucleotide metabolism and nitrogen management. Additionally, sulphate-containing metabolites differentiated Bd21 and Bd3-1 lines in spikes. Structural analysis based on MS fragmentation spectra enabled identification of 93 specialized metabolites. Among them phenylpropanoids and flavonoids derivatives were mainly determined. As compared with closely related barley and wheat species, metabolic profile of Brachypodium is characterized with presence of threonate derivatives of hydroxycinnamic acids.     

Intermolecular Interactions and Spectroscopic Signatures of the Hydrogen-Bonded System—n-Octanol in Experimental and Theoretical Studies

n-Octanol is the object of experimental and theoretical study of spectroscopic signatures and intermolecular interactions. The FTIR measurements were carried out at 293 K for n-octanol and its deuterated form. Special attention was paid to the vibrational features associated with the O-H stretching and the isotope effect. Density Functional Theory (DFT) in its classical formulations was applied to develop static models describing intermolecular hydrogen bond (HB) and isotope effect in the gas phase and using solvent reaction field reproduced by Polarizable Continuum Model (PCM). The Atoms in Molecules (AIM) theory enabled electronic structure and molecular topology study. The Symmetry-Adapted Perturbation Theory (SAPT) was used for energy decomposition in the dimers of n-octanol. Finally, time-evolution methods, namely classical molecular dynamics (MD) and Car-Parrinello Molecular Dynamics (CPMD) were employed to shed light onto dynamical nature of liquid n-octanol with emphasis put on metric and vibrational features. As a reference, CPMD gas phase results were applied. Nuclear quantum effects were included using Path Integral Molecular Dynamics (PIMD) and a posteriori method by solving vibrational Schrödinger equation. The latter applied procedure allowed to study the deuterium isotope effect.     

Recovery of Metals from Electronic Waste-Printed Circuit Boards by Ionic Liquids,DESs and Organophosphorous-Based Acid Extraction

The extraction of metals from waste printed circuit boards (WPCBs) with ionic liquids (ILs), Deep Eutectic Solvents (DESs) and organophosphorous-based acid (Cyanex 272) has been presented. The study was undertaken to assess the effectiveness of the application of the new leaching liquids, and the new method of extraction of metals from the leachate and the solid phase with or without the leaching process. Solvent extraction from the liquid leachate phase has been studied in detail with popular ILs, such as tetraoctylphosphonium bromide, {[P_8,8,8,8][Br] and tributyltetradecylphosphonium chloride, [P_4,4,4,14][Cl] using Aqueous Biphasic Systems (ABS) method. Trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate, [P_6,6,6,14][Cyanex272], ([P_6,6,6,14][BTMPP]), trihexyltetradecylphosphonium thiocyanate, [P_6,6,6,14][SCN], methyltrioctylammonium chloride (Aliquat 336), as well as bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272) were also used in the extraction of metals from the leachate. Two DESs (1) {choline chloride + lactic acid, 1:2} and (2) {choline chloride + malonic acid, 1:1} were used in the extraction of metals from the solid phase. The extraction behavior of metals with DESs was compared with that performed with three new bi-functional ILs: didecyldimethylammonium salicylate, [N_10,10,1,1][Sal], didecyldimethylammonium bis(2-ethylhexyl) phosphate, [N_10,10,1,1][D2EHPA], and didecyldimethylammonium bis(2,4,4-trimethylpentyl) phosphinate, [N_10,10,1,1][Cyanex272]. The [P_6,6,6,14][Cyanex272]/toluene and (Cyanex 272 + diethyl phosphite ester) mixtures exhibited a high extraction efficiency of about 50–90% for different metal ions from the leachate. High extraction efficiency of about 90–100 wt% with the ABS method using the mixture {[P_8,8,8,8][Br], or [P_4,4,4,14][Cl] + NaCl + H₂O₂ + post-leaching liquid phase} was obtained. The DES 2 revealed the efficiency of copper extraction, E_Cu = 15.8 wt% and silver, E_Ag = 20.1 wt% at pH = 5 from the solid phase after the thermal pre-treatment and acid leaching. The solid phase extraction efficiency after thermal pre-treatment only was (E_Cu = 9.6 wt% and E_Ag = 14.2 wt%). The use of new bi-functional ILs did not improve the efficiency of the extraction of metal ions from the solid phase. Process factors such as solvent concentration, extraction additives, stripping and leaching methods, temperature, pH and liquid/solid as well as organic/water ratios were under control. For all the systems, the selectivity and distribution ratios were described. The proposed extraction processes can represent alternative paths in new technologies for recovering metals from electronic secondary waste.     

A Study on the Chemistry and Biological Activity of 26-Sulfur Analogs of Diosgenin: Synthesis of 26-Thiodiosgenin S-Mono- and Dioxides,and Their Alkyl Derivatives

A chemoselective procedure for MCPBA oxidation of 26-thiodiosgenin to corresponding sulfoxides and sulfone was elaborated. An unusual equilibration of sulfoxides in solution was observed. Moreover, α-alkylation of sulfoxide and sulfone was investigated. Finally, the biological activity of obtained compounds was examined.     

Simultaneous monitoring of monoamines,amino acids,nucleotides and neuropeptides by liquid chromatography‐tandem mass spectrometry and its application to neurosecretion in bovine chromaffin cells

The primary functions of adrenal medullary chromaffin cells are the synthesis and storage in their chromaffin vesicles of the catecholamines noradrenaline (NA) and adrenaline (AD), and their subsequent release into the bloodstream by Ca²⁺‐dependent exocytosis under conditions of fear or stress (fight or flight response). Several monoamines, nucleotides and opiates, such as leucine‐enkephalin (LENK) and methionine‐enkephalin (MENK), are also co‐stored and co‐released with the catecholamines. However, other neurotransmitters have not been studied in depth. Here, we present a novel high‐resolution liquid chromatography‐tandem mass spectrometry approach for the simultaneous monitoring of 14 compounds stored and released in bovine chromaffin cells (BCCs). We validated the analytical method according to the recommendations of the EMA and FDA by testing matrix effect, selectivity, sensitivity, precision, accuracy, stability and carry‐over. After testing on six batches of BCCs from different cultures, the method enabled simultaneous quantitative determination of monoamines (AD, NA, dopamine, serotonin, 5‐hydroxyindoleacetic acid, histamine and metanephrine), amino acids (L‐glutamic acid, γ‐aminobutyric acid), nucleotides (adenosine 5′‐diphosphate, adenosine 5′‐monophosphate, cyclic adenosine 5′‐monophosphate) and neuropeptides (LENK and MENK) in the intracellular content, basal secretion and acetylcholine induced secretion of BBCs. The high‐resolution approach used here enabled us to determine the levels of 14 compounds in the same BCC batch in only 16 min. This novel approach will make it possible to study the regulatory mechanisms of Ca²⁺ signaling, exocytosis and endocytosis using different neurotrophic factors and/or secretagogues as stimuli in primary BCC cultures. Our method is actually being applied to human plasma samples of different therapeutic areas where sympathoadrenal axis is involved in stress situations such as Alzheimer's disease, migraine or cirrhosis, to improve diagnosis and clinical practice. Copyright © 2016 John Wiley & Sons, Ltd.     

Hydration of simple amides. FTIR spectra of HDO and theoretical studies

The hydration of formamide (F), N-methylformamide (NMF), N,N-dimethylformamide (DMF), acetamide (A), N-methylacetamide (NMA), and N,N-dimethylacetamide (DMA) has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure has been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To facilitate the interpretation of obtained spectral results, DFT calculations of aqueous amide clusters were performed. Molecular dynamics (MD) simulation for the cis and trans forms of NMA was also carried out for the SPC model of water. Infrared spectra reveal that only two to three water molecules from the surrounding of the amides are statistically affected, from among ca. 30 molecules present in the first hydration sphere. The structural-energetic characteristic of these solute-affected water molecules differs only slightly from that in the bulk and corresponds to the clathrate-like hydrogen-bonded cage typical for hydrophobic hydration, with the possible exception of F. MD simulations confirm such organization of water molecules in the first hydration sphere of NMA and indicate a practical lack of orientation and energetic effects beyond this sphere. The geometry of hydrogen-bonded water molecules in the first hydration sphere is very similar to that in the bulk phase, but MD simulations have affirmed subtle differences recognized by the spectral method and enabled their understanding. The spectral data and simulations results are highly compatible. In the case of F, NMF, and A, there is a visible spectral effect of water interactions with N-H groups, which have destabilizing influence on the amides hydration shell. There is no spectral sign of such interaction for NMA as the solute. The energetic stability of water H-bonds in the amide hydration sphere and in the bulk fulfills the order: NMA > DMA > A > NMF > bulk > DMF > F. Microscopic parameters of water organization around the amides obtained from the spectra, which have been used in the hydration model based on volumetric data, confirm the more hydrophobic character of the first three amides in this sequence. The increased stability of the hydration sphere of NMA relative to DMA and of NMF relative to DMF seems to have its origin in different geometries, and so the stability, of water cages containing the amides.     

Equations of second order in time with quasilinear damping: existence in Orlicz spaces via convergence of a full discretisation

A nonlinear evolution equation of second order with damping is studied. The quasilinear damping term is monotone and coercive but exhibits anisotropic and nonpolynomial growth. The appropriate setting for such equations is that of monotone operators in Orlicz spaces. Global existence of solutions in the sense of distributions is shown via convergence of the backward Euler scheme combined with an internal approximation. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and reactions of the thioamide derivatives of methyl vinyl ketone

The reaction of isothiocyanates with in situ generated carbanions of α,β‐unsaturated ketones yielded α,β‐unsaturated keto thioamides which in the reaction with acids or bases cyclized to give 2,6‐disubstituted thiopyran‐4‐ones and in the reaction with α‐bromoesters gave thiazolidin‐4‐one derivatives. The thiopyran‐4‐ones reacted with α,β‐unsaturated aldehydes to yield tetrahydrothiopyran[2,3‐b]pyridin‐4‐ones, while thioanilides were formed in the reaction with phenyl isothiocyanate.     

Collagen Hydrolysate Prepared from Chicken By-Product as a Functional Polymer in Cosmetic Formulation

Chicken stomachs can be processed into collagen hydrolysate usable in cosmetic products. The aim of the study was to verify the effects of a carbopol gel formulation enriched with 1.0% (w/w) chicken hydrolysate on the properties of the skin in the periorbital area after regular application twice a day for eight weeks in volunteers ageed 50 ± 9 years. Skin hydration, transepidermal water loss (TEWL), skin elasticity and skin relief were evaluated. Overall, skin hydration increased by 11.82% and 9.45%, TEWL decreased by 25.70% and 17.80% (always reported for the right and left area). Generally, there was an increase in skin elasticity, a decrease in skin roughness, as the resonance times decreased by 85%. The average reduction of wrinkles was 35.40% on the right and 41.20% on the left. For all results, it can be seen that the longer the cosmetic gel formulation is applied, the better the results. Due to the positive effect on the quality and functionality of the skin, it is possible to apply the cosmetic gel formulation in the periorbital area. The advantage of the product with chicken collagen hydrolysate is also the biocompatibility with the skin and the biodegradability of the formulation.