Model dipeptides incorporating the trans cyclohexane analogues of phenylalanine: further evidence of the relationship between side-chain orientation and β-turn type

In order to study the influence of the side-chain orientation on the peptide backbone conformation we have synthesised the model dipeptides t-BuCO-l-Pro-(1S,2R)-c₆Phe-NHMe and t-BuCO-l-Pro-(1R,2S)-c₆Phe-NHMe, incorporating each enantiomer of the trans cyclohexane analogue of phenylalanine (trans-1-amino-2-phenylcyclohexanecarboxylic acid). The orientation of the aromatic side-chain determines the β-turn type accommodated by these peptides to the point that the (1S,2R)-c₆Phe derivative retains the type I β-turn in the crystalline state, in contrast to the behaviour exhibited by the natural counterpart t-BuCO-l-Pro-l-Phe-NHMe.     

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.     

Synthesis and photophysical evaluations of β-fused uracil-porphyrin derivatives

New β-fused uracil-porphyrin conjugates were synthesized by the tetramerization of uracil-pyrroles under acidic conditions. Two different synthetic approaches were systematically studied in order to evaluate their efficiency, as well as the possibility to obtain a single regioisomer. Metallation effects were studied for aggregation in solution, and preliminary photophysical experiments were also performed in order to evaluate the potential of these new compounds.     

Comparison of low-order multireference many-body perturbation theories

Tests have been made to benchmark and assess the relative accuracies of low-order multireference perturbation theories as compared to coupled cluster (CC) and full configuration interaction (FCI) methods. Test calculations include the ground and some excited states of the Be, H(2), BeH(2), CH(2), and SiH(2) systems. Comparisons with FCI and CC calculations show that in most cases the effective valence shell Hamiltonian (H(v)) method is more accurate than other low-order multireference perturbation theories, although none of the perturbative methods is as accurate as the CC approximations. We also briefly discuss some of the basic differences among the multireference perturbation theories considered in this work.     

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.     

Highly Diastereoselective [3+2] Cycloadditions Between Non-Racemic p-Tolylsulfinimines and Iminoesters: An Efficient Entry to Enantiopure Imidazolidines and Vicinal Diaminoalcohols

Abstract

Readily available p-tolylsulfinimines undergo highly stereoselective [3 + 2] cycloadditions with azomethine ylides generated from α -iminoesters and LDA to produce N-sulfinylimidazolidines. In the presence of Lewis acids, p-tolylsulfinimines react with glycine iminoester enolates to produce N-sulfinylimidazolidines, after cyclization of open chain intermediates. These mechanistically diverse processes take place with excellent regio-, stereo-, and facial selectivities, and the latter is opposite to most known reactions involving sulfinimines. Some of the resulting imidazolidines have been transformed into examples of a novel class of nonsymmetrical vicinal diamines using reductive and/or hydrolytic protocols.     

Structural Basis for Carbapenemase Activity of the OXA-23 β-Lactamase from Acinetobacter baumannii

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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.     

Capillary electrophoretic separation of serum proteins of workers occupationally exposed to heavy metals

Metallurgy processes are associated with many hazardous and toxic factors, including heavy metals. Exposure to heavy metals can cause damage to different organs, which can be observed through variation in the concentration of proteins in serum. The aim of this study was to evaluate the changes in a serum protein profile of copper smelters exposed to As, Cd and Pb ions, and xenobiotics present in tobacco smoke. A 2.3-fold higher Pb concentration in the blood and a 2.8-fold greater As concentration have been observed in the urine of non-smoking smelters compared to a control group. In the blood of smoking smelters, Cd concentration was 2-fold higher than in non-smoking ones. Serum proteins were separated by capillary electrophoresis, and in the group of non-smoking smelters, a higher amount of α₁-globulins was observed. In the group of smoking smelters, fewer α₁-globulins were noted. Furthermore, a greater amount of α₂-globulins in the serum of smoking and non-smoking workers in relation to the control group was revealed. A positive correlation between the concentration of Cd in the blood and the content of a fraction containing α₁- and α₂-globulins was revealed. Urine Cd concentration was found to be negatively associated with the α₁- and α₂-globulins fraction. Observed abnormalities in the proteins profiles of smelters can be important markers when assessing exposure to heavy metals and in the early diagnosis of diseases caused by them.