DFT studies on tautomeric preferences. Part 3: Proton transfer in 2-(8-acylquinolin-2-yl)-1,3-diones

8-Acetyl- and 8-benzoyl-2-(quinolin-2-yl) derivatives of 1,3-diketones were studied from point of view of their tautomeric preferences. Effective electron delocalization and strong hydrogen bonds were found to be responsible for high stability of the enaminone form (the most stable tautomer). Density functional theory (DFT) calculations prove that enolimine and ketimine species are less favored. Contribution of the zwitterionic resonance structures to the enaminone form is most significant in 2-(quinolin-2(1H)-ylidene)-2H-indene-1,3-dione derivatives. Formation of the bifurcated hydrogen bonds was found to take place only in 8-acetyl derivatives. One of these bonds is of the RAHB (Resonance Assisted Hydrogen Bond) type. There is a steric interaction of the pyridine β-hydrogen and carbonyl oxygen atoms in the enaminone tautomers.     

Crystallographic evidence of Gly‐d,l‐Met oxidation to its sulfoxide in the presence of gold(III): solid solution of the racemic mixture of two diastereoisomers

Crystallographic analysis of a solid solution of two diastereoisomers, i.e. ({(1S,R)‐1‐carboxy‐3‐[(R,S)‐methylsulfinyl]propyl}aminocarbonyl)methanaminium tetrachloridoaurate(III) and ({(1S,R)‐1‐carboxy‐3‐[(S,R)‐methylsulfinyl]propyl}aminocarbonyl)methanaminium tetrachloridoaurate(III), (C₇H₁₅N₂O₄S)[AuCl₄], has shown that in the presence of gold(III), the methionine part of the Gly‐d ,l ‐Met dipeptide is oxidized to sulfoxide, and no coordination to the Au^III cation through the S atom of the sulfoxide is observed. In view of our observation, literature reports that methionine acts as an N,S‐bidentate donor ligand forming stable gold(III) complexes require verification. Moreover, it has been demonstrated that crystallization of the oxidation product leads to a substantial 77:23 excess of both S‐methionine/R‐sulfoxide and R‐methionine/S‐sulfoxide over S‐methionine/S‐sulfoxide and R‐methionine/R‐sulfoxide. The presence of two different diastereoisomers at the same crystallographic site is a source of static disorder at this site.     

Comparison of protein precipitation methods for various rat brain structures prior to proteomic analysis

Sample preparation is a fundamental step in proteomic methodologies. The quality of the results from a proteomic experiment is dependent on the nature of the sample and the properties of the proteins. In this study, various pre-treatment methods were compared by proteomic analysis; we analysed various rat brain structures after chloroform/methanol, acetone, TCA/acetone and TCA protein precipitation procedures. The protein content of the supernatant was also examined by 2-DE. We found that for four of the rat brain structures, precipitation with chloroform/methanol and acetone delivered the highest protein recovery for top-down proteomic analysis; however, TCA precipitation resulted in good protein separation and the highest number of protein spots in 2-DE. Moreover, TCA precipitation also gave high efficiency of protein recovery if prior sonication procedure was performed.     

Dispersive liquid–liquid microextraction applied to isolation and concentration of alkylphenols and their short-chained ethoxylates in water samples

Dispersive liquid–liquid microextraction (DLLME) coupled with high-performance liquid chromatography with fluorescence detector was applied for the determination of alkylphenols and their short-chained ethoxylates in water samples. Development of DLLME procedure included optimisation of some important parameters such as kind and volume of extracting and dispersing solvents. Under optimised conditions 50 μL of trichloroethylene in 1.5 mL of acetone were rapidly injected into 5 mL of a water sample. After centrifuging the organic phase containing the analytes was taken for evaporation with a gentle nitrogen purge and reconstituted to 50 μL of acetonitrile. The aliquot of this solution was analysed with the use of HPLC. For octylphenol (OP) and octylphenol ethoxylates (OPEOs) linearity was satisfactory in the range 8–1000 μg L⁻¹ and for nonylphenol (NP) and nonylphenol ethoxylates (NPEOs) linearity was in the range from 50 to about 3000 μg L⁻¹. Limit of quantitation was 0.1 μg L⁻¹ for OP and OPEOs and 0.3 μg L⁻¹ for NP and NPEOs. Satisfactory recoveries between 66 and 79% were obtained for environmental samples. The results showed that DLLME is a simple, rapid and sensitive analytical method for the preconcentration of trace amounts of alkylphenols and their ethoxylates in environmental water samples.     

Reverse engineering of Al<Subscript>x</Subscript>Ga<Subscript>1−x</Subscript>As/GaAs structures composition by reflectance spectroscopy

The paper presents the application of non-modulation reflectance method for composition profiling of epitaxial Al_xGa_−xAs/GaAs structures. This non-destructive method is based on spectral measurements and theoretical reflectance spectrum matching. This is a very accurate and sensitive method of determining the Al composition in Al_xGa_1−xAs layers and structures with resolution down to 1 nm. In this work, the authors describe theoretic principles of this method and present experimental results of characterization of different AlGaAs structures to prove the potential of the worked out method.     

On variable discounting in dynamic programming: applications to resource extraction and other economic models

This paper generalizes the classical discounted utility model introduced in Samuelson (Rev. Econ. Stud. 4:155–161, 1937) by replacing a constant discount rate with a function. The existence of recursive utilities and their constructions are based on Matkowski’s extension of the Banach Contraction Principle. The derived utilities go beyond the class of recursive utilities studied in the literature and enable a discussion on subtle issues concerning time preferences in the theory of finance, economics or psychology. Moreover, our main results are applied to the theory of optimal economic growth related with resource extraction models with unbounded utility function of consumption.     

Quasi-Banach spaces of almost universal disposition

We show that for each p∈(0,1]$p\in (0,1]$ there exists a separable p  -Banach space _Gp${\mathbb{G}}_p$ of almost universal disposition, that is, having the following extension property: for each ε>0$\epsilon >0$ and each isometric embedding g:X→Y$g:X\to Y$, where Y is a finite-dimensional p-Banach space and X   is a subspace of _Gp${\mathbb{G}}_p$, there is an ε  -isometry f:Y→_Gp$f:Y\to {\mathbb{G}}_p$ such that x=f(g(x))$x=f(g(x))$ for all x∈X$x\in X$.