Computation of Oxidation Potentials of Solvated Nucleobases by Static and Dynamic Multilayer Approaches

The determination of the redox properties of nucleobases is of paramount importance to get insight into the charge-transfer processes in which they are involved, as those occurring in DNA-inspired biosensors. Although many theoretical and experimental studies have been conducted, the value of the one-electron oxidation potentials of nucleobases is not well defined. Moreover, the most appropriate theoretical protocol to model the redox properties has not been established yet. In this work, we have implemented and evaluated different static and dynamic approaches to compute the one-electron oxidation potentials of solvated nucleobases. In the static framework, two thermodynamic cycles have been tested to assess their accuracy against the direct determination of oxidation potentials from the adiabatic ionization energies. Then, the introduction of vibrational sampling, the effect of implicit and explicit solvation models, and the application of the Marcus theory have been analyzed through dynamic methods. The results revealed that the static direct determination provides more accurate results than thermodynamic cycles. Moreover, the effect of sampling has not shown to be relevant, and the results are improved within the dynamic framework when the Marcus theory is applied, especially in explicit solvent, with respect to the direct approach. Finally, the presence of different tautomers in water does not affect significantly the one-electron oxidation potentials.

Extraction concentrating of the acid-soluble forms of rare earth elements from oils of the Volga-Ural oil and gas province using rotating coiled columns

Trace elements in oils are the natural markers of the oil origin of and the mechanism of oil genesis. Direct determination of rare earth elements (REE) in crude oils is rather difficult due to their low concentrations (10–6 wt. %). Information about the forms of trace elements in oils is of particular interest. The goal of the study is determination of the content of acid-soluble forms of REE in oils from various fields of the Volga-Ural oil and gas province. Six samples of oils of heavy and medium density and viscosity were analyzed. Extraction of acid-soluble forms of REE was carried out using rotating coiled columns in 0.5 M aqueous solution of nitric acid. Toluene was used to dilute the oils up to the necessary values of the density and viscosity providing the possibility of extraction in the system aqueous acid solution – oil. The content of REE was determined by inductively coupled plasma mass spectrometry on an Agilent 7900 spectrometer. Their content in an acid-soluble form in oil samples under study ranged within 172 – 2173 ng/kg. Such a wide range of values is attributed to the difference in the geology and age of deposit formation. The highest content of acid-soluble forms of REE (2173 ng/kg) was observed in the oil sample from the Novo-Elkhovsky field, whereas the lowest value (172 ng/kg) was measured in the oil sample of the Pioneer field. It is shown that the content of acid-soluble forms of REE depends on tectonic zoning, productive horizons and layers, as well as on the physical and chemical properties of oils. The distribution of acid-soluble forms of light and heavy REE was evaluated. Most of the REE (75 – 99%) determined in the analyzed oil samples are light REE. It is noted that systematization of the data on the properties of oils, geological and geochemical characteristics of the deposits will provide reliable forecasting of the various forms of REE present in oils.

Intercomparison of different state-of-the-art formulations of the mass density of humid air

The differences between one classical and three state-of-the-art formulations of the mass density of humid air were quantified. Here, we present both the calculi for direct determination of the humid-air mass density employing the virial form of the thermodynamic equation of state, and a sufficiently accurate look-up-table for the quick-look determination of the humid-air mass density, which is based on the advanced Thermodynamic Equation of Seawater 2010.

Approaches to liquid chromatography tandem mass spectrometry assessment of glyphosate residues in wine

The performance of two different analytical methodologies to investigate the presence of glyphosate (GLY) and aminomethylphosphonic acid (AMPA) residues in wine samples was evaluated. Transformation of compounds in their fluorene-9-methyloxycarbonyl derivatives permitted their separation under reversed-phase liquid chromatography with tandem mass spectrometry (LC–MS/MS) determination. Although the wine matrix severely impaired the efficiency of GLY derivatization, this drawback was solved using a molecularly imprinted sorbent for the previous, selective extraction of GLY and AMPA from wine. Alternatively, the use of a strong anionic exchange, polyvinyl alcohol-based LC column, turned to be the most effective alternative for direct determination of both compounds in diluted wine samples. The chromatographic behavior of this column and the magnitude of matrix effects observed during analysis of diluted wine samples were significantly affected by the composition of the mobile phase. Under final working conditions, this column permitted the separation of AMPA and the fungicide fosetyl (which shows common transitions in tandem MS/MS methods), it improved significantly the sample throughput versus extraction-derivatization-purification method, and it allowed the use of solvent-based calibration standards. Both analytical procedures provided similar limits of quantification (LOQs) for GLY (0.5–1.0 ng mL−1), while the multistep method was 8 times more sensitive to AMPA than the direct procedure. GLY residues stayed above method LOQs in 70% of the processed wines; however, concentrations measured in 95% of positive samples remained 100 times below the maximum residue limit (MRL) set for GLY in vinification grapes. Graphical abstract

Impacts of Soil Properties, Topography, and Environmental Features on Soil Water Holding Capacities (SWHCs) and Their Interrelationships

Soil water holding capacities (SWHCs) are among the most important factors for understanding the water cycle in forested catchments because they control available plant water that supports evapotranspiration. The direct determination of SWHCs, however, is time consuming and expensive, so many pedotransfer functions (PTFs) and digital soil mapping (DSM) models have been developed for predicting SWHCs. Thus, it is important to select the correct soil properties, topographies, and environmental features when developing a prediction model, as well as to understand the interrelationships among variables. In this study, we collected soil samples at 971 forest sites and developed PTF and DSM models for predicting three kinds of SWHCs: saturated water content (θS) and water content at pF1.8 and pF2.7 (θ1.8 and θ2.7). Important explanatory variables for SWHC prediction were selected from two variable importance analyses. Correlation matrix and sensitivity analysis based on the developed models showed that, as the matric suction changed, the soil physical and chemical properties that influence the SWHCs changed, i.e., soil structure rather than soil particle distribution at θS, coarse soil particles at θ1.8, and finer soil particle at θ2.7. In addition, organic matter had a considerable influence on all SWHCs. Among the topographic features, elevation was the most influential, and it was closely related to the geological variability of bedrock and soil properties. Aspect was highly related to vegetation, confirming that it was an important variable for DSM modeling. Information about important variables and their interrelationship can be used to strengthen PTFs and DSM models for future research.

Laminar Burning Velocity of Lean Methane/Air Flames under Pulsed Microwave Irradiation

Laminar burning velocity of lean methane/air flames exposed to pulsed microwave irradiation is determined experimentally as part of an effort to accurately quantify the enhancement resulting from exposure of the flame to pulsed microwaves. The experimental setup consists of a heat flux burner mounted in a microwave cavity, where the microwave has an average power of up to 250 W at an E-field in the range of 350–380 kV/m. Laminar burning velocities for the investigated methane/air flames increase from 1.8 to 12.7% when exposed to microwaves. The magnitude of the enhancement is dependent on pulse sequence (duration and frequency) and the strength of the electric field. From the investigated pulse sequences, and at a constant E-field and average power, the largest effect on the flame is obtained for the longest pulse, namely 50 μs. The results presented in this work are, to the knowledge of the authors, the first direct determination of laminar burning velocity on a laminar stretch-free flame exposed to pulsed microwaves.