Several novel sulfides from acetone extracts of bulbs of garlic (Allium sativum L.), were identified and investigated. These were named garlicnins B 1 (1), C 1 (2), and D (3), and they were found to have the ability to control macrophage activation. Garlicnins B 1 (1) and C 1 (2) possess a new skeleton of cyclic sulfoxide and their structures of garlicnins B 1 (1) and C 1 (2) were characterized as 3,4-dimethyltetrahydrothiophene-Soxide derivatives carrying the substitutions of a propenyl and a sulfenic acid, and an allyldithiine and a 1-propene-sulfenic acid (a), respectively. The mechanism of the proposed production of these compounds is discussed. Garlicnin D (3), dithiine-type, was estimated to be derived by addition of (a) allyl thiosulfenic acid (b) derived from allicin. The identification of these novel sufoxides from onion and garlic accumulates a great deal of new chemistry to the Allium sulfide field, and future pharmacological investigations aid the development of natural, healthy foods and anti-cancer agents that could potentially prevent or combat disease.Key words Allium sativum; sulfoxide; garlicnin B 1 ; garlicnin C 1 ; garlicnin D; macrophage activation Garlic, Allium sativum L. (Liliaceae) is at the top of the National Cancer Institute's list of designer foods that prevent cancer. The various biological activities of garlic are generally classified into two cases, cardiovascular disease prevention and cancer prevention. For the former, activities include the inhibition of cholesterol synthesis, platelet aggregation, and arterial smooth muscle cell proliferation inhibition as well as having anti-inflammatory, anti-oxidant, and hydrogen sulfide-mediated vasodilatory effects. Effects on carcinogen metabolism (enhanced cellular glutathione synthesis induced cell cycle arrest and apoptosis) and prevention of Helicobacter pylori infection, gastric cancer, and colorectal cancer make up the latter category.1-3) The chemistry of garlic sulfides is summarized in a text book editted by Block. 3,4) In previous work, we isolated a novel, stable sulfide, 3,4-dimethyl-5-(1-propenyl)-tetrahydrothiophene-2-sulfoxide-S-oxide, from the acetone extract of Allium cepa L. which was found to inhibit macrophage activation. We named this onionin A. 5)Here, sulfur-containing substances from an acetone-soluble extract of A. sativum L. have been isolated and characterized to aid the development of natural, healthy foods that potentially prevent and combat disease, in particular tumors.Chinese garlic (1061 g) was roughly chopped and blended in a mixer along with acetone. Subsequently, the mixture was soaked in acetone for 3 d at room temperature. The filtrate was evaporated at 40°C in vacuo to obtain a residue (26.1 g), which was then subjected to polystyrene gel column chromatography (Diaion HP-20). It was first eluted with water, then with methanol (residue after evaporation: 5.90 g), and finally with acetone (the residue after evaporation: 0.32 g). Part of the methanolic eluate (3.0 g) was partitioned between ethyl ace...

The increasing incidence of atopic dermatitis during recent decades has prompted the development of safe and effective agents for prevention of atopic diseases. Esculeoside A, a glycoside of spirosolane type, is identified as a major component in ripe tomato fruits. The present study investigated the effects of esculeoside A and its aglycon esculeogenin A on hyaluronidase activity in vitro and antiallergy in experimental dermatitis mice. Esculeogenin A/esculeoside A (esculeogenin A equivalent) with an IC50 of about 2 μM/9 μM dose-dependently inhibited hyaluronidase activity measured by a modified Morgan-Elson method. Oral treatment with esculeoside A 10 mg/kg of experimental dermatitis mice for 4 weeks significantly decreased the skin clinical score to 2.5 without any detectable side effects compared with 6.75 of the control. The scratching frequency of esculeoside A 100 mg/kg application was decreased significantly as 107.5 times compared with 296.67 times of the control. Thus, the present study showed that esculeoside A/esculeogenin A significantly blocks hyaluronidase activity in vitro and that esculeoside A ameliorates mouse experimental dermatitis.

Separation and structural determination of the chloroform-soluble components obtained from the peels of the persimmon (Diospyros kaki Thunb.) were performed. β-Carotene, lycopene, β-cryptoxanthin monomyristic acid ester, zeaxanthin di-myristic acid ester, the latter two of which were accompanied by a small amount of palmitoleic acid in the fatty acid moiety, and oleanolic acid were identified. Among these components, the mono-fatty acid ester of β-cryptoxanthin and the di-fatty acid ester of zeaxanthin were characterized for the first time.Key words persimmon peel; carotenoid; β-cryptoxanthin mono-fatty acid ester; zeaxanthin di-fatty acid ester; myristic acid; palmitoleic acidThe persimmon Diospyros kaki Thunb. is a fruit that is indigenous to Japan, and China, Korea, and Japan produce most of the fruits used for commercial consumption. Persimmons (Kaki) are also used traditionally for medicinal purposes, because of their preventive action against infection, diabetes, and arteriosclerosis, and because of their diuretic effect.1) The persimmon contains many compounds such as different sugars, starch, organic acids, ascorbic acid, tannins, flavonoids, carotenoids, triterpenoids, and fatty acids.2-7) With regard to its pharmacological activities, many studies have reported pharmacological effects including antioxidant activity and tyrosinase inhibitory activity. 3,[8][9][10] The peels of fresh astringent persimmons are usually removed and dried, which yields sweet dried persimmon peels. The peel was found to contain more polyphenols 11) and carotenoids 12) than the fruit body. The persimmon flesh contained large amounts of carotenoids, which are responsible for the color of the fruits.4,5) Unlike vitamin C and vitamin E, β-carotene and other carotenoids can scavenge singlet oxygen.13) Also, carotenoids are known to exist as free compounds or as fatty acid esters in plants. Because the peels of persimmons are usually discarded, we believe that it might be possible to recover the peels for industrial utilization or for use as a food supplement.Breithaupt and Bamedi 14) suggested, on the basis of HPLC results, the occurrence of carotenoid esters as β-cryptoxanthin ester and zeaxanthin ester in persimmons. Weller and Breithaupt 15) also suggested, on the basis of LC/MS results, the presence of zeaxanthin esters as diesters of dipalmitate and of palmitate and stearate in persimmons. However, they did not isolate these compounds as pure single entities. Differences in the chemical structure of each carotenoid and its ester would lead to different pharmacological effects and physicochemical characteristics. For example, synthetic lutein myristate ester was more stable than free lutein after heat or UV treatment. 16)Sugawara et al. 17) found that Caco-2 cells easily took up more hydrophobic carotenoids than less hydrophobic carotenoids. One can easily envision that different carotenoids with or without ester moieties would have different polar characteristics and that differences in structure would lead to different bioch...

Italian canned tomatoes contain the tomato glycosides esculeosides B-1 (1, 0.0052%) and B-2 (2, 0.0068%) without esculeoside A. Herein, the structure of esculeoside B-1 (1) is characterized to be 3-O-β-lycotetraosyl (5S,22R,23S,25S)-22,26-epimino-16β,23-epoxy-3β,23,27-trihydroxycholestane 27-O-β-d-glucopyranoside. We hypothesized that these substances might be derived from esculeoside A when the cans are prepared with treatment in boiling water. To confirm that hypothesis, we refluxed esculeoside A with water for 6.5 h, providing esculeosides B-1 (1) and B-2 (2) in yields of 25.8% and 31.0%, respectively. Key words Solanum lycopersicum; canned tomato; tomato saponin; esculeoside A; esculeoside B-1; esculeoside B-2In 2003, Nohara and colleagues 1,2) isolated a tomato saponin, called esculeoside A, from the ripe fruits of tomato, Solanum lycopersicum L. and determined its structure ( Fig. 1). Tomato saponin is a significant component of ripened tomatoes and occurs at levels approximately 4-fold higher than those of lycopene. Thus far, the bioactivity of tomato has been attributed solely to lycopene. Therefore, carrying out pharmacological examinations of esculeoside A in the near future is important.Recently, Fujiwara et al. 3) have revealed that oral administration of esculeoside A to apolipoprotein E-deficient mice significantly reduces levels of serum cholesterol glycerides, low-density lipoprotein-cholesterol and the areas of atherosclerotic lesions without any detectable side effects. Our recent studies on the constituents of Solanum plants have revealed that pregnane glycosides are accompanied by normal spirostanol and furostanol glycosides [4][5][6][7][8][9][10][11][12] ; esculeogenin A is easily converted into a pregnane derivative by refluxing with aqueous pyridine, 13) and pregnane glycoside has been obtained from the over-ripe tomato fruit. 14) These facts strongly suggest that orally administered steroidal glycosides can be metabolized into pregnane derivatives, which are a type of steroidal hormone.Therefore, in further experiments, men consumed tomatoes and their urine was collected and separated with various column chromatographies to afford 3 androstane derivatives. 15)These androsterone analogs are normally excreted; however, because no excretions were detected in the control samples, the occurrence of androsterone analogs indicated excretion via the production of progesterone by subjects that had consumed tomatoes. The tomato steroidal glycoside might stimulate the hormone secretor or perhaps is itself metabolized into the pregnane. We hypothesize that orally administered steroidal glycosides such as spirostanol, furostanol and spirosolane glycosides are metabolized, introducing a hydroxyl group at C-23. These intermediates may then be metabolized into pregnane derivatives.Thus, we conclude that the tomato saponin esculeoside A

A tomato saponin, esculeoside A, may be metabolized into various steroidal hormones such as pregnane derivatives that are expected to exhibit various bioactivities in the body, such as anti-osteoporosis, anti-menopausal disorder and anti-tumor actions. Therefore, we attempted to examine the esculeoside A contents of fresh tomatoes, tomatoes boiled in water, tomatoes heated using a microwave oven, freeze-dried tomatoes, and commercially available processed tomato products contained in plastic bottles and cans, in order to develop a health food.