Eco-friendly rapid synthesis of 3-substituted-2-thioxo-2,3-dihydroquinazolin-4(1H)-ones in choline chloride based deep eutectic solvent

A series of 3-substituted-2-thioxo-2,3-dihydroquinazolin-4(1H)-ones and 6-iodo-3-substituted-2-thioxo-2,3-dihydroquinazolin-4(1H)-ones were synthesized in choline chloride/urea deep eutectic solvent. Substituted 2-mercapto-4(3H)-quinazolinones were synthesized from anthranilic acid or 5-iodoanthranilic acid and appropriate isothiocyanates in good to excellent yields. Isolation of final product was easy and required no further purification. Synthesis of these compounds was rapid, selective, and catalyst free, while preparation of deep eutectic solvent was easy, components are readily available, cheap, and environmentally friendly.     

On the cycle-dependence of topological resonance energy

The topological resonance energy (TRE) was conceived in the 1970s. From the very beginning, it was known that TRE is equal to the collective energy-effect of all cycles present in a conjugated molecule. Also in the 1970s a theory of cyclic conjugation was elaborated, by means of which it was possible to compute the energy-effect ef(Z) of each individual cycle Z present in a conjugated molecule. Yet, the connection between TRE and the ef(Z)-values was, until now, not studied. We now show that TRE and the sum of the ef(Z)-values are closely correlated but that a certain correction needs to be made by taking into account the energy-effects of pairs, triplets, quartets, etc. of cycles.     

Determination of the soil-to-grass transfer of 137Cs and its relation to several soil properties at various locations in Serbia

Transfer coefficients of (137)Cs from soil to grass were determined for the terrain around the city of Kragujevac in central Serbia. Mass activity concentrations of (137)Cs in soil and grass samples were determined with a high-purity Ge-detector (HPGe). The activity concentration at the depth of 20 cm was found to be in the range of 14.92-124.05 Bq kg(-1), whereas the activity in grass for the same location was in the range of 4.60-84.95 Bq kg(-1). Transfer factors (TFs) were in the range of 0.07 up to 1.94. Dependences of TFs on different soil characteristics were presented graphically. Weak dependences were determined between them. Absalom's model was used to predict TFs based on soil characteristics: pH value, contents of clay, exchangeable potassium and humus. A comparison of measured and predicted values from Absalom's model is shown graphically. It has been found that Absalom's model might be carefully used for the prediction of (137)Cs in grass for specific regions.     

Pyridyl‐Functionalised 3H‐1,2,3,4‐Triazaphospholes: Synthesis,Coordination Chemistry and Photophysical Properties of Low‐Coordinate Phosphorus Compounds

Novel conjugated, pyridyl‐functionalised triazaphospholes with either tBu or SiMe₃ substituents at the 5‐position of the N₃PC heterocycle have been prepared by a [3+2] cycloaddition reaction and compared with structurally related, triazole‐based systems. Photoexcitation of the 2‐pyridyl‐substituted triazaphosphole gives rise to a significant fluorescence emission with a quantum yield of up to 12 %. In contrast, the all‐nitrogen triazole analogue shows no emission at all. DFT calculations indicate that the 2‐pyridyl substituted systems have a more rigid and planar structure than their 3‐ and 4‐pyridyl isomers. Time‐dependent (TD) DFT calculations show that only the 2‐pyridyl‐substituted triazaphosphole exhibits similar planar geometry, with matching conformational arrangements in the lowest energy excited state and the ground state; this helps to explain the enhanced emission intensity. The chelating P,N‐hybrid ligand forms a Re^I complex of the type [(N^N)Re(CO)₃Br] through the coordination of nitrogen atom N² to the metal centre rather than through the phosphorus donor. Both structural and spectroscopic data indicate substantial π‐accepting character of the triazaphosphole, which is again in contrast to that of the all‐nitrogen‐containing triazoles. The synthesis and photophysical properties of a new class of phosphorus‐containing extended π systems are described.     

Additive results for the Drazin inverse of block matrices and applications

In this paper, we consider the Drazin inverse of a sum of two matrices and derive additive formulas under conditions weaker than those used in some recent papers on the subject. As a corollary we get the main results from the paper of Yang and Liu [H. Yang, X. Liu, The Drazin inverse of the sum of two matrices and its applications, J. Comput. Appl. Math. 235 (2011) 1412-1417]. As an application we give some new representations for the Drazin inverse of a block matrix.     

Aminotroponiminate zinc complexes as catalysts for the intramolecular hydroamination

This review deals with the synthesis of aminotroponiminate and aminotroponate zinc complexes. The main focus is on their application as catalysts for the intramolecular hydroamination, in which good activity, particularly high functional group tolerance and a relatively high stability towards moisture and air were observed. In addition, a heterogeneous zinc catalyst was reported in order to increase the stability and the recyclability of the catalytic system.     

Feasibility of the internal standardization in direct determination of arsenic in wine samples by inductively coupled plasma atomic emission spectrometry

In this study, a fast and simple method is proposed for determination of arsenic in wine employing inductively coupled plasma atomic emission spectroscopy and internal standard technique. First Co, Bi, V and Y were evaluated as internal standards to minimize transport interferences. All samples and reference solutions were automatically spiked by autosampler, eliminating the need for manual dilutions. The result demonstrated that vanadium can be used as an internal standard. The experimental parameters (plasma power and nebulization flow rate) were optimized. The relative standard deviations (R.S.D) of measurements varied from 1.1 to 6.0% and 3.2 to 8.7% (n = 12) with and without internal standardization, respectively. Recoveries in the 95-103% range for As spiked samples were obtained.     

Enhanced membrane transport of pharmaceutically active protic ionic liquids

We show that pharmaceutically active protic ionic liquids can be designed to rapidly transport through model membranes as neutral hydrogen bonded clusters.     

Quantification of 15-F2t-isoprostane in human plasma and urine: results from enzyme-linked immunoassay and liquid chromatography/tandem mass spectrometry cannot be compared

Quantification of F(2)-isoprostanes is considered a reliable index of the oxidative stress status in vivo. Several immunoassays and chromatography/mass spectrometry-based assays are available for 15-F(2t)-isoprostane quantification. However, it remains unclear if results of immunoassays using different assays can be compared with those of liquid chromatography/mass spectrometry (LC/MS) assays. Previous studies comparing enzyme-linked immunosorbent assay (ELISA) and more specific gas chromatography/mass spectrometry assays have already indicated that ELISAs may overestimate 15-F(2t)-isoprostane concentrations in human plasma. Concentrations of 15-F(2t)-isoprostane in 25 human plasma and urine samples were measured by three commercially available ELISA assays (Assay Designs, Cayman Chemical and Oxford Biomedical Research) and compared with the concentrations measured with a validated, semi-automated high-throughput HPLC tandem mass spectrometry assay (LC/LC-MS/MS). All three ELISAs measured substantially higher 15-F(2t)-isoprostane concentrations (2.1-182.2-fold higher in plasma; 0.4-61.9-fold higher in urine) than LC/LC-MS/MS. Utilization of solid-phase extraction (SPE) columns, especially isoprostane affinity purification columns, brought ELISA isoprostane urine concentrations closer to the LC/LC-MS/MS results. However, SPE did not have much of an effect on ELISA plasma concentrations which remained significantly higher than corresponding LC/LC-MS/MS results. A poor correlation not only between LC/LC-MS/MS and immunoassay results, but also among the immunoassays was found. Especially in plasma, ELISAs grossly overestimate 15-F(2t)-isoprostane concentrations and are not comparable with each other or with LC/LC-MS/MS. It is most disturbing that a sample with relatively high concentrations measured with one ELISA may show low concentrations with another ELISA, and vice versa, potentially affecting the conclusions drawn from such data. The use of specific mass spectrometry-based assays seems advisable.     

Development and validation of a reversed-phase HPLC method for determination of alkaloids from Papaver somniferum L. (Papaveraceae)

An HPLC method for the separation of six target alkaloids from Papaver somniferum L. (morphine, codeine, oripavine, thebaine, papaverine, and noscapine) was developed, optimized, and validated. The chromatographic behavior of these alkaloids was investigated using a reversed-phase chromatography at acidic and alkaline pH. The effects of ion-pairing agents, pH value of the mobile phase, concentration of the buffer components, mobile phase organic modifier, and column temperature were studied. Regardless of the large differences in their pKa values, all alkaloids were separated within a close retention window, and good peak shape was achieved for each of the six alkaloids. The proposed method has adequate selectivity, linearity, accuracy, precision, and reproducibility and is applicable for poppy straw.