Clear and cloudy apple juices from Idared and Champion varieties were studied for their radicalscavenging effects. The polyphenolic content and composition of the juices before and after thiolysis were determined by high-performance liquid chromatography with diode array detection. Cloudy juices, especially that prepared from Champion variety, had a higher content of procyanidins than clear juices. Radical-scavenging activity was measured by electron paramagnetic resonance (EPR) spectroscopy using the stable 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. All juices showed long-lasting radical-scavenging activity, and EPR spectra were recorded over time to follow the reaction kinetics. Scavenging of DPPH showed pseudo-first-order kinetics, which might be expected in the presence of polymerised antioxidants that prevent closer contact between the DPPH radical and hydroxyl groups. The content of polymeric procyanidins showed a linear dependence on the rate constant, suggesting that these compounds are mainly responsible for time-extended radical-scavenging activity. The antioxidant properties of apple juices were much better reproduced by EPR spectroscopy than by UV-visible measurements. The former method is especially sensitive to the concentration of polymerised or bound procyanidins, whilst the latter method requires transparent (clear) samples. Apple juices, especially cloudy ones, are a rich source of natural antioxidants that may be used in the pharmaceutical or food industry.

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The validity of the chromane helicity rule correlating the sense of twist within the dihydropyran ring with the CD sign of the (1)Lb band observed at ca. 290 nm in their electronic circular dichroism (ECD) spectra is examined using a set of natural (S)-trolox derivatives. To investigate both the scope and the limitations of the rule a combination of ECD spectroscopy, especially the temperature dependence of the ECD spectra, single crystal X-ray diffraction analyses, and density functional theory (DFT) calculations was used. A thorough conformational analysis supported by the X-ray data led to the identification of predominant conformers. Then, a comparison of the experimental ECD spectra with the spectra simulated by TDDFT calculations allowed for a reasonable interpretation of the accumulated data. The results clearly indicated that to avoid the possibility of erroneous conclusions the chromane helicity rule should be used with great caution. This is likely related to the conformational flexibility of tested compounds by which conformers of different helicities can be produced. Therefore, based on the results presented here, it is strongly recommended that the conclusions derived from analysis of experimental data are supported with the appropriate theoretical computations.

Three flavonoids of pharmaceutical importance-baicalein, baicalin, and wogonoside-were isolated from a Chinese medicinal plant Scutellaria baicalensis Georgi and studied by 13C NMR in solution and solid state. Two-dimensional (2D) NMR spectroscopy in the liquid phase and dipolar dephasing (DD) experiments in magic-angle spinning (MAS) spectra enabled the assignment of 13C resonances. The cross-polarization (CP) time constants T(CH) and relaxation times T(H) (1rho) were obtained from the variable-contact time experiments. The principal elements of the 13C chemical shift tensor were determined in the spectra recorded under slow sample spinning (2 kHz) using phase-adjusted spinning sideband (PASS)-2D NMR technique, and were verified by density functional theory gauge-independent atomic orbital (DFT GIAO) calculations of shielding constants. Analysis of the 13C delta(ii) and comparison with shielding parameters calculated for different conformers of compounds 1-3 enabled the selection of the most reliable geometry in the solid phase. In all three compounds, an intramolecular hydrogen bond C5--OH...=C4 is formed; the existence of baicalein and baicalin with 'anticlockwise' orientation of OH groups is more probable.