Experimental and Theoretical DFT Study on Synthesis of Sterically Crowded 2,3,3,(4)5‐Tetrasubstituted‐4‐nitroisoxazolidines via 1,3‐Dipolar Cycloaddition Reactions Between Ketonitrones and Conjugated Nitroalkenes

1,3‐Dipolar cycloaddition reactions between ketonitrones ( 1a , 1b , 1c , 1d , 1e ) and β‐substituted nitroalkenes ( 2a , 2b , 2c , 2d ) proceed under mild conditions, with complete regioselectivity, and lead with high yields to sterically crowded 2,3,3,5‐tetrasubstituted‐4‐nitroisoxazolidines ( 3a , 3b , 3c , 3d , 3e , 3f ). Reaction course may be interpreted on the basis of nature of local, nucleophile–electrophile interactions. Moreover, density functional theory (DFT) simulations of reaction paths suggest that these reactions should be considered as polar, “one‐step two‐stage” cycloadditions. Subsequently, it has been found that similar reactions between ketonitrones and α‐substituted nitroalkenes do not allow to obtain the expected 2,3,3,4‐tetrasubstituted‐4‐nitroisoxazolidines.     

Chemical Composition and Antioxidant Activity of the Leaf Essential Oil of Cryptocarya amygdalina

Chemistry of Natural Compounds -     

Moisture Resistance,Thermal Stability and Fire Behavior of Unsaturated Polyester Resin Modified with L-histidinium Dihydrogen Phosphate-Phosphoric Acid

In this paper, the fire behavior of unsaturated polyester resin (UP) modified with L-histidinium dihydrogen phosphate-phosphoric acid (LHP), being a novel intumescent fire retardant (IFR), was investigated. Thermal and thermomechanical properties of the UP with different amounts of LHP (from 10 to 30 wt. %) were determined by thermogravimetric analysis (TG) as well as dynamic mechanical thermal analysis (DMTA). Reaction to small flames was studied by horizontal burning (HB) test, while fire behavior and smoke emission were investigated with the cone calorimeter (CC) and smoke density chamber. Further, the analysis of volatile products was conducted (TGA/FT-IR). It was observed that the addition of LHP resulted in the formation of carbonaceous char inhibiting the thermal decomposition, burning rate and smoke emission. The most promising results were obtained for the UP containing 30 wt. % of LHP, for which the highest reduction in maximum values of heat release rate (200 kW/m²) and total smoke release (3535 m²/m²) compared to unmodified polymer (792 kW/m² and 6895 m²/m²) were recorded. However, some important disadvantage with respect to water resistance was observed.     

On ordering and multiplication of natural numbers

Even if the ordering of all natural number is (known to be) not definable from multiplication of natural numbers and ordering of primes, there is a simple axiom system in the language such that the multiplicative structure of positive integers has a unique expansion by a linear order coinciding with the standard order for primes and satisfying the axioms – namely the standard one. Received: 3 December 1998     

Insight into the influence of terminal ligands on magnetic exchange coupling in a series of dimeric copper(II) acetate adducts

A combination of experimental (SQUID magnetometry) and quantum-chemical (BS-DFT, CASSCF(n,m)/NEVPT2, DDCI3) methods is used to probe the influence of terminal ligands on magnetic exchange coupling in the series of [Cu₂(μ₂-OAc)₄L₂] complexes with O-donor terminal ligands extended by two novel complexes containing phosphine oxide ligands. The possibilities and limitations of these approaches are discussed. The influence of terminal ligands on magnetic superexchange interaction was quantified by two contributions—the first contribution is associated with structural changes within the {Cu(μ₂-OAc)₄Cu} core, while the second contribution is due to the difference in the electronic influence of different terminal ligands at a given core geometry. Both contributions were found to be approximately of the same order of magnitude. These results indicate that magnetic exchange coupling, known to be highly sensitive to the distortions in core geometry, is not solely determined by the core structure. Our findings are consistent with the fact that various one- and multiparameter magnetostructural correlations reported in the literature have only a qualitative predictive capability.     

The synthesis and spectral properties of new DNA binding ligands

Two new ligands based on anthracene or carbazole planar skeletons, and a phenyloxazoline moiety linked by a vinyl bridge are synthesized as potential DNA-interacting drugs. Their spectral characteristics and DNA binding affinity are assessed.     

Preparation of samples for alpha-spectrometry by direct evaporation of extracted species

Because of the energy loss of α-particles by self-absorption, α-spectrometry requires thin, uniform, and nearly weightless samples. Several methods exist for sample preparation, e.g., electrodeposition or co-precipitation. Unfortunately, the methods yielding the best energy resolution are not always quantitative and are usually relatively demanding and time-consuming. This fact makes application of α-spectrometry for screening tests with radiotracers complicated. For its simplicity and fastness, the possibility to prepare samples for α-spectrometry by direct evaporation of simple aliquots of aqueous or organic solutions and the influence of the presence of volatile organic diluent or tensioactive agent was investigated. Also, the influence of coating the samples with Mylar film was evaluated. The sample preparation techniques were compared based on the counting efficiency and energy resolution achieved. The performance of the selected method was tested on assessment of the efficiency of americium extraction by BTBP (bis-triazine-bipyridine) extractant.     

Streamlining sample preparation and gas chromatography–tandem mass spectrometry analysis of multiple pesticide residues in tea

In this work, a new rapid method for the determination of 135 pesticide residues in green and black dry tea leaves and stalks employing gas chromatography coupled to tandem mass spectrometry (GC–MS/MS) with a triple quadrupole was developed and validated. A substantial simplification of sample processing prior to the quantification step was achieved: after addition of water to a homogenised sample, transfer of analytes into an acetonitrile layer was aided by the addition of inorganic salts. Bulk co-extracts, contained in the crude organic extract obtained by partition, were subsequently removed by liquid–liquid extraction using hexane with the assistance of added 20% (w/w) aqueous NaCl solution. The importance of matrix hydration prior to the extraction for achieving good recoveries was demonstrated on tea samples with incurred pesticide residues. For most of the analytes, recoveries in the acceptable range of 70–120% and repeatabilities (relative standard deviations, RSDs) ≤20% were achieved for both matrices at spiking levels of 0.01, 0.1 and 1 mg kg⁻¹. Under optimised GC–MS/MS conditions, most of the analytes gave lowest calibration level ≤0.01 mg kg⁻¹, permitting the control at the maximum residue levels (MRLs) laid down in Regulation (EC) No 396/2005. The developed method was successfully applied to the determination of pesticide residues in real tea samples.     

Asymmetric Kinugasa reaction involving six-membered cyclic nitrones

Kinugasa reactions between terminal acetylenes and six-membered ring nitrones when one or both components are chiral, proceed in a low to moderate yield and with a high diastereoselectivity affording mostly one, dominant β-lactam product. The first step of the reaction is controlled by the configuration of the nitrone, whereas the protonation of the C-7 center of the carbacepham skeleton in the second step depends on: a) the configuration of the bridgehead carbon atom formed in the first step, b) epimerization process in the presence of a base, and c) on the configuration of the stereogenic center in the acetylenic partner. In the case of the nitrone derived from dihydroisoquinoline, the reaction proceeds in a more complex way affording not only β-lactams, but also products derived from the alternative regio-1,3-cycloaddition, or nucleophilic addition of the acetylene to the double bond of the nitrone.     

Isobavachalcone as an Active Membrane Perturbing Agent and Inhibitor of ABCB1 Multidrug Transporter

Isobavachalcone (IBC) is an active substance from the medicinal plant Psoralea corylifolia. This prenylated chalcone was reported to possess antioxidative, anti-inflammatory, antibacterial, and anticancer activities. Multidrug resistance (MDR) associated with the over-expression of the transporters of vast substrate specificity such as ABCB1 (P-glycoprotein) belongs to the main causes of cancer chemotherapy failure. The cytotoxic, MDR reversing, and ABCB1-inhibiting potency of isobavachalcone was studied in two cellular models: human colorectal adenocarcinoma HT29 cell line and its resistant counterpart HT29/Dx in which doxorubicin resistance was induced by prolonged drug treatment, and the variant of MDCK cells transfected with the human gene encoding ABCB1. Because MDR modulators are frequently membrane-active substances, the interaction of isobavachalcone with model phosphatidylcholine bilayers was studied by means of differential scanning calorimetry. Molecular modeling was employed to characterize the process of membrane permeation by isobavachalcone. IBC interacted with ABCB1 transporter, being a substrate and/or competitive inhibitor of ABCB1. Moreover, IBC intercalated into model membranes, significantly affecting the parameters of their main phospholipid phase transition. It was concluded that isobavachalcone interfered both with the lipid phase of cellular membrane and with ABCB1 transporter, and for this reason, its activity in MDR cancer cells was presumptively beneficial.