The dihydrochalcone derivatives of the bitter flavonoids naringin and neohesperedin are intensely sweet. Phyllodulcin is as sweet as the dihydrochalcones with similar taste properties although its structure apparently resembles that of bitter flavanone or flavone. Multifaceted approaches, including X-ray crystal structure analysis, energy calculation, and structure comparison, have been employed to clarify the structure-taste correlations in these classes of compounds. In the crystal, naringin dihydrochalcone assumes a 'J'-shaped conformation with a fully-extended dihydrochalcone moiety while neohesperidin dihydrochalcone assumes the same overall conformation but with a partially-extended moiety. A 2D conformational energy map of dihydrochalcone obtained using molecular mechanics revealed nine local minima. The pseudoequatorial and pseudoaxial forms of phyllodulcin have the same AM1 energies with a low energy barrier between them. The partially-extended form of dihydrochalcone and the pseudoequatorial form of phyllodulcin which are the maximally superposable conformers are proposed to be the active conformers. The major difference between the structures of flavone and phyllodulcin is not in the overall planarity but in the relative orientation of the pyrone and phenyl ring systems.

η 3 -Allyliridium(III) complexes Cp*Ir(η 3 -CHPhCHCH 2 )(-CtC-t-Bu) (2), Cp*Ir(η 3 -CHPh-CHCH-CHdCH(t-Bu))Cl (3H), Cp*Ir(η 3 -CHPhCHCH-CHdCMe(t-Bu))I (3Me), [Cp*Ir(η 3 -CHPhCHCH-CHdCMe(t-Bu))(NCMe)] + (4), and Cp*Ir(η 3 -CHPhCHCH-CHdCMe(t-Bu))-(-CtC-t-Bu′) (5) have been prepared from the reactions of [Cp*Ir(η 3 -CHPhCHCH 2 )-(NCMe)] + (1) with H-CtC-t-Bu (in the presence of NEt 3 ), HCl, and MeI. The crystal structures of 2 and 5 have been determined by X-ray diffraction data analyses. Reactions of 3 and 5 with HCl produce trans,trans-1,3-pentadienes, PhCHdCHCHdCHCH 2 (t-Bu) (6H) and PhCHdCHCHdCHCHMe(t-Bu) (6Me), and cis,trans,trans-1,3,5-heptatriene, (t-Bu′)-CHdCHC(Ph)dCHCHdCHCHMe(t-Bu) (8), respectively. ResultsSynthesis of Metal Complexes. Alkynyl η 3 -allyl complex Cp*Ir(η 3 -CHPhCHCH 2 )(-CtC-t-Bu) (2) is prepared by replacing MeCN with -CtC-t-Bu from the reaction of H-CtC-t-Bu with [Cp*Ir(η 3 -CHPhCHCH 2 )-(NCMe)] + (1) in the presence of NEt 3 and characterized by spectral and elemental analysis data and also by crystal structure determination by X-ray diffraction analysis (Figure 1). The η 3 -allyl group of 2 in the solid state is best described as a symmetric η 3 -allyl ligand since the C-C distances (C(11)-C(12) 1.44(2) Å; C(12)-C(13) 1.38(2) Å) in the η 3 -allyl group are not much different from each other. 1 H NMR spectrum of 2 in CDCl 3 shows typical signals due to an η 3 -allyl lignd. 3a,7 Complex 2 reacts with HCl and MeI to give the η 3pentadienyl-iridium complexes Cp*Ir(η 3 -CHPhCHCH-CHdCH(t-Bu))Cl (3H) and Cp*Ir(η 3 -CHPhCHCH-CHd CMe(t-Bu))I (3Me), respectively (see Scheme 1). The Iin 3Me is readily replaced by MeCN to give [Cp*Ir(η 3 -CHPhCHCH-CHdCMe(t-Bu))(NCMe)] + (4), which further undergoes substitution reaction of MeCN with another -CtC-t-Bu′ group to produce Cp*Ir(η 3 -CHPh-CHCH-CHdCMe(t-Bu))(-CtC-t-Bu′) (5) in the presence of NEt 3 (see Scheme 1).These η 3 -pentadienyl-iridium complexes 3-5 have been unambiguously characterized by spectral and elemental analysis data and also by crystal structure

Several recent clinical trials have demonstrated that lower plasma cholesterol levels do indeed have a beneficial effect on events related to coronary heart diseases. (Fig. 1) were isolated from the culture of fungus strain F1064, that was isolated from a soil sample collected at Mt. Jiree, Kyun-815 gnamProvince, Korea. It was taxonomically identified as Trichothecium roseum by the method of Pitt and Hocking.9) A 2-ml portion of the seed culture was inoculated into a 1-liter baffled flask with four baffles containing 100 ml of production medium (soluble starch 2%, soytone 0,4%, pharmamedia 0.3%, K2HPO4 0.1%, 0.05%, NaCl 0.2%, CaCO3 0.3%, FeSO4-7H2O 0.002%, MnCl2-4H2O 0.001%, ZnSO4-7H2O 0.01%, CoCl2 0.005%). The fermentation was carried out for 5days at 26°C on a rotary shaker at 150 rpm. After fermentation at 26°C for 5days, the whole broth (800ml) was centrifuged to obtain the mycelial part which was extracted with 900ml of acetone. After filtration and concentration of the acetone extract, the resulting aqueous solution (100ml) was extracted twice with 500ml of chloroform. The extracts were concentrated in vacuo to dryness to give brown oily materials (1.5g).The oily material was applied to a silica gel column (30 g). The materials were eluted with a stepwise gradient of w-hexane-ethyl acetate. Active fractions were concentrated in vacuo to yield pale brown oily material

Seungmagalgeuntang (SG) is broadly used in traditional Oriental medicine especially in Korea, China, and Japan, for its many pharmacological effects. This study was carried out to investigate the antioxidative, antimicrobial, and anticytotoxic activities of SG and fermented seungmagalgeuntang (FSG). DPPH radical scavenging activities of SG and FSG were 70% and 74%, respectively, which increased slightly by fermentation. Nitrite scavenging activities were strongly altered at pH 1.2, (36.4% in SG and 38.3% in FSG) by addition of 200 μg/g. Superoxide dismutase-like activities were from 21.5% to 23.3% at a concentration of 0.4 mg/mL, and the highest value were observed in FSG. Total flavonoid contents of SG and FSG were 47.1 and 52.1 μg/L, respectively which shows an increase upon fermentation. In the antimicrobial activity test, MIC50 values of SG and FSG were 800 μg/mL for Candida albicans and 3,200 and 1,600 μg/mL for Staphylococcus epidermidis and Staphylococcus aureus, respectively. Antibacterial effects were higher in FSG compared to SG. Anticytotoxic cadmium toxicities ranged from 63.5% to 76.1% at 10 μg/mL of SG and FSG, and the highest value was observed in FSG. In the sensory evaluation, color, flavor, and overall preference values were higher in FSG.