Copper(II) complexes with a flexible oxamato ligand

We report on a convenient synthesis of the ligand precursor, diethylethylene-1,2-bis(oxamate), (Et₂H₂oeo, 1), and show how a partial and preferential hydrolysis of the ester group can give rise to the dianionic ligand, (H₂oeo)²⁻. Reaction of this ligand with Cu(II) affords the neutral dimeric species, [Cu₂(H₂oeo)₂], which has a low aqueous solubility. We describe the crystal structure of the hydrate Cu₂(H₂oeo)₂(H₂O)₄ (2) and report magnetic studies that show a weak exchange interaction in the solid. Under more basic conditions and in the presence of Cu(II) ions, we are able to avoid amide cleavage and yet deprotonate the amide group, resulting in the formation of the highly soluble [Cu(Hoeo)₂]⁴⁻ complex anion. The structure of (NBu₄)₄[Cu(Hoeo)₂](H₂O)₄ (3) is described and compared with the recently reported anhydrous phase.     

Artificial neural networks for quantification in unresolved capillary electrophoresis peaks

The application of the combination of experimental design (ED) and artificial neural networks (ANNs) for the quantification of overlapped peaks in capillary zone electrophoresis is described. When the total separation cannot be achieved by separation techniques, the use of ED-ANN can be a suitable approach. The unstability of EOF causes peak shift that has to be corrected in order to apply ED-ANN methods. In this work, normalization procedure of electropherograms with consequent application of ANNs for quantification purpose was developed. Both, spectra and electropherograms can be used as multivariate data. In general, both kinds of data were found to be suitable for unresolved peaks quantification by ED-ANN approach.     

The direct detection of a hydrogen bond in the solid state by NMR through the observation of a hydrogen-bond mediated (15)N [bond] (15)N J coupling

A new method for detecting hydrogen bonds in the solid state is presented. Using two-dimensional NMR correlation experiments, it is shown that a hydrogen-bond mediated J coupling can be observed in a powder under magic-angle spinning conditions, even though the J coupling is 2 orders of magnitude smaller than the dominant anisotropic interactions encountered in solid-state NMR. Specifically, the observation of a pair of peaks in a two-dimensional 15N-15N solid-state INADEQUATE experiment due to two nitrogens that have no covalent connectivity is attributed to the presence of a J coupling across a linking hydrogen bond.     

Two Intercalation Mechanisms of Oxazole Yellow Dimer (YOYO-1) into DNA

The oxazole yellow dye, YOYO-1 (a symmetric homodimer), is a commonly used molecule for staining DNA. We applied the brightness analysis to study the intercalation of YOYO-1 into the DNA. We distinguished two binding modes of the dye to dsDNA: mono-intercalation and bis-intercalation. Bis-intercalation consists of two consecutive mono-intercalation steps, characterised by two distinct equilibrium constants (with the average number of base pair per binding site equals 3.5): K1=3.36±0.43×107M−1 and K2=1.90±0.61×105M−1, respectively. Mono-intercalation dominates at high concentrations of YOYO-1. Bis-intercalation occurs at low concentrations.     

Modular Breath Analyzer (MBA): Introduction of a Breath Analyzer Platform Based on an Innovative and Unique,Modular eNose Concept for Breath Diagnostics and Utilization of Calibration Transfer Methods in Breath Analysis Studies

Exhaled breath analysis for early disease detection may provide a convenient method for painless and non-invasive diagnosis. In this work, a novel, compact and easy-to-use breath analyzer platform with a modular sensing chamber and direct breath sampling unit is presented. The developed analyzer system comprises a compact, low volume, temperature-controlled sensing chamber in three modules that can host any type of resistive gas sensor arrays. Furthermore, in this study three modular breath analyzers are explicitly tested for reproducibility in a real-life breath analysis experiment with several calibration transfer (CT) techniques using transfer samples from the experiment. The experiment consists of classifying breath samples from 15 subjects before and after eating a specific meal using three instruments. We investigate the possibility to transfer calibration models across instruments using transfer samples from the experiment under study, since representative samples of human breath at some conditions are difficult to simulate in a laboratory. For example, exhaled breath from subjects suffering from a disease for which the biomarkers are mostly unknown. Results show that many transfer samples of all the classes under study (in our case meal/no meal) are needed, although some CT methods present reasonably good results with only one class.     

Physicochemical and Quality Properties of Dried Courgette Slices: Impact of Vacuum Impregnation and Drying Methods

The aim of this study was to determine the effects that the type of impregnating solution and drying method (freeze drying (FD) and vacuum drying (VD) at 45 °C and convective drying (CD) at 50, 60, and 70 °C) had on the physicochemical and quality properties of courgettes. Courgette slices were vacuum-impregnated (6 kPa) in freshly squeezed onion, kale, and onion and kale (50:50) juices with 3% NaCl solution (N). The application of vacuum impregnation (VI) with impregnating solutions from freshly squeezed onions and kale had a beneficial effect on the bioactive values of courgette. The highest contents of quercetin (41.84 μg/g d.m.) and carotenoids (276.04 μg/g d.m.) were found in courgette impregnated with onion juice after freeze drying. The highest values of lutein and zeaxanthin (216.42 μg/g d.m.) were recorded for courgette impregnated with kale juice and convective dried. By analysing the kinetics of convective drying, the best matching of the logistic model was found. Increasing the drying process temperature from 50 to 70 °C reduced the drying time from 15% to 36%, depending on the type of impregnating solution used. Water activity < 0.6 was recorded for courgette dried by freezing, vacuum, and convection at 60 and 70 °C. Conclusions: The vacuum impregnation process and the impregnation solutions from freshly squeezed vegetables can be used to develop new snacks with high levels of bioactive compounds. The FD method is the most appropriate considering both the bioactive compounds content and the obtained colour and water activity.     

Pyrolysis study of hydrophobic tholins By TG-MS, TG, DTA and DSC methods

This study presents the thermogravimetry (TG) of hydrophobic tholins, obtained from different simulation experiments of prebiotic synthesis carried out in a CH₄/N₂/H₂ atmosphere with spark discharge activation of aqueous aerosols and liquid water. Differential thermal analysis and differential scanning calorimetry were also used to evaluate the thermal behaviour of these complex organic compounds that could play an important role in prebiotic chemistry. A coupled thermogravimetry-mass spectrometry system allowed us to analyse the principal volatile thermal decomposition and fragmentation products of the hydrophobic tholins under dynamic conditions and an inert atmosphere. During their thermal degradation, which occurs in two stages, a wide variety of hydrocarbon products including methane, vinyl monomers (such as ethylene and propylene), acetylene, oligomers, and some other unknown compounds are found. Besides, a thermally stable structure is present (graphitic structure) in these particular organic substances. Finally, data collected from TG experiments in an oxidative atmosphere showed significant differences at temperatures above 240 °C. According to these results, the different techniques of thermal analysis here applied have proved to be an adequate methodology for the study and characterization of these complex systems, structures of which remain controversial even in these days.     

Pyrolysis-gas chromatography-mass spectrometry of cured phenolic resins

A previously described pyrolysis device with a movable reaction zone was used in the present work for thermal degradation of cured novolac and resol resins. After the pyrolysis the usual major components were identified, as well as relatively low-volatile aromatic compounds which were revealed after their separation in a capillary chromatographic column. Among the latter components, for both types of cured resins, xanthene and its methyl derivatives were found. The isomers of bis(hydroxyphenyl)methane were found in considerable quantities only in the case of partially cured novolac resins which contained any linear sequences in their structure.     

Stereodifferentiation of chiral compounds using reversed-phase liquid chromatography coupled with capillary gas chromatography

A method is described for the enantiomeric quantitation of some chiral compounds via online coupling of reversed-phase liquid chromatography-gas chromatography. The evaluation of some variables affecting the experimentation (i.e., the packing material used in the interface, volume of the transferred fraction, desorption time, initial temperature of the interface, and purge time) makes it possible to optimize the recoveries obtained for some chiral terpenes and lactones using a capillary column of beta-cyclodextrin dissolved in OV-1701. The proposed method allows the enantiomeric analysis of aqueous matrices obtaining relative standard deviations lower than 9% and detection limits ranging from 0.26-0.93 ppm for the investigated compounds.     

Tandem RCM-Pauson-Khand reaction for access to tricycles in one step

Starting from conveniently designed dienynes complexed to cobalt, a tandem RCM-intramolecular Pauson-Khand reaction yields tricyclic compounds. The methodology allows the synthesis of 6,5,5 and 7,5,5 systems.