Glycosides of benzyl and salicyl alcohols from Alangium chinense.

From the water-soluble fraction of the dried leaves of Alangium chinense, three new glycosides, benzyl alcohol beta-D-glucopyranosyl-(1 --> 2)-[beta-D-xylopyranosyl-(1 --> 6)]-beta-D-glucopyranoside, 2'-O-beta-D-glucopyranosylsalicin, and 2'-O-beta-D-glucopyranosyl-6'-O-beta-D-xylopyranosylsalicin were isolated along with seven known glycosides. The structures of the new compounds were determined by spectroscopic and chemical means.

Tetrahydroisoquinoline-monoterpene and iridoid glycosides from Alangium lamarckii.

From the water soluble fraction of the dried fruits of Alangium lamrckii, four tetrahydroisoquinoline-monoterpene glycosides, 6-O-methyl-N-deacetylisoipecosidic acid, 7-O-methyl-N-deacetylisoipecosidic acid, 6,7-di-O-methyl-N-deacetylisoipecosidic acid and 6"-O-alpha-D-glucopyranosyl-6-O-methyl-N-deacetylisoipecosidic acid, and an iridoid glycoside, 6'-O-alpha-D-glucopyranosylloganic acid, were isolated, together with six known compounds. The structures of the previously unknown compounds were determined by spectroscopic and chemical means. The significance of these glucosides in the biogenesis of Alangium alkaloids is discussed; 6-O-methyl-N-deacetylisoipecosidic acid was also chemically converted into 10-O-demethylprotoemetine and dihydroisoalangine.

Influence of natural and synthetic compounds on cell surface expression of cell adhesion molecules, ICAM-1 and VCAM-1.

Various natural and synthetic compounds including alkaloids, terpenoids and phenolics were tested for inhibition of the cell surface expression of intercellular adhesion molecule-1 (ICAM-1) and vascular cell adhesion molecule-1 (VCAM-1), both of which are crucial in the regulation of immune response and inflammation. Of 40 compounds tested, two compounds significantly downregulated the expression of VCAM-1 on murine endothelial cells (F-2) and ten compounds that of ICAM-1 on mouse myeloid leukemia cells (M1). Sanguinarine chloride (5) and isoliquiritigenin (13) were capable of lowering the levels of both ICAM-1 and VCAM-1. The structure-activity relationships study on chalcone and flavone derivatives related to 13 suggested that the inhibitory activity of the chalcone derivatives is attributable to the 4-hydroxy group as well as the possible coplanarity between the phenyl ring and the adjacent conjugated ketone.

Two Alangium alkaloids from Alangium lamarckii.

Two new Alangium alkaloids, 1',2'-dehydrotubulosine (1) and alangine (2), were isolated from the dried fruits of Alangium lamarckii along with tubulosine (3), isotubulosine (4), deoxytubulosine, cephaeline, isocephaeline, psychotrine, neocephaeline, 10-O-demethylcephaeline, 2'-N-(1"-deoxy-1" -beta-D-fructopyranosyl)cephaeline, protoemetine, protoemetinol, salsoline, and alangiside. The structures of the new alkaloids (1 and 2) were determined by spectroscopic and chemical means.

Quaternary isoquinoline alkaloids from Stephania cepharantha.

From the quaternary alkaloidal fraction of the dried tubers of Stephania cepharantha, two new isoquinoline alkaloids, stecepharine and tetradehydroreticuline have been isolated along with the known compounds, magnoflorine, menisperine, steponine, cyclanoline, oblongine, cis-N-methylcapaurine and 2'-N-methylisotetrandrine. cis-N-Methylcapaurine (=9-O-methylstecepharine) was isolated as a natural product for the first time. Their structures were determined on the basis of spectroscopic evidence.

A tetrahydroisoquinoline-monoterpene glucoside and an iridoid glucoside from Alangium kurzii.

From the leaves of Alangium kurzii, a new tetrahydroisoquinoline-monoterpene glucoside, 6-O-methyl-N-deacetylipecosidic acid and a new iridoid glucoside, 10-O-benzoyladoxosidic acid, were isolated along with alangiside, demethylalangiside, 6''-O-beta-D-glucosylhenryoside, uridine and four known flavonoid glycosides. The structures of new glucosides were determined on the basis of spectroscopic and chemical methods.

Five phenolic glycosides from Alangium chinense.

From the dried leaves of Alangium chinense, five novel phenolic glycosides, 6'-O-galloylsalicin (1); 4',6'-di-O-galloylsalicin (2); 4',6'-O-(S)-hexahydroxydiphenoylsalicin (3); 4', 6'-O-(R)-hexahydroxydiphenoylsalicin (4); and pyrocatechol 1-O-beta-D-xylopyranosyl(1-->6)-beta-D-glucopyranoside (5) were isolated. The structures of these new compounds were determined by spectroscopic methods.

Three secoiridoid glucosides from Jasminum nudiflorum.

Phytochemical study of the leaves and stems of Jasminum nudiflorum has led to the isolation of three secoiridoid glucosides, jasnudiflosides A-C (1-3). The structures of these compounds were elucidated on the basis of chemical and spectroscopic evidence.

Ipecac alkaloids from Cephaelis acuminata.

From the dried roots of Cephaelis acuminata, five ipecac alkaloids, neocephaeline, 7'-O-demethylcephaeline, 10-O-demethylcephaeline, 2'-N-(1"-deoxy-1"-beta-D-fructopyranosyl)cephaeline and 2'-N-(1"-deoxy-1"-beta-D-fructopyranosyl)neocephaeline, were isolated, along with emetine, cephaeline, psychotrine, protoemetine, 9-demethylprotoemetinol and isocephaeline. Structures were determined by spectroscopic and chemical means.

Bisbenzylisoquinoline alkaloids from Stephania cepharantha and their effects on proliferation of cultured cells from the murine hair apparatus.

Bisbenzylisoquinoline alkaloids were isolated from Stephania cepharantha Hayata and their proliferative activities on cultured hair cells from the murine skin were evaluated. Cepharanthine (1), cepharanoline (9), isotetrandrine (2), and berbamine (7) showed significant activities in the range of 0.01-0.1 microgram/ml, but had no activity on cultured keratinocytes or fibroblasts from the murine skin.

An iridoid glucoside from Jasminum hemsleyi.

A new iridoid glucoside, jashemsloside E, was isolated from the leaves of Jasminum hemsleyi. Its structure was elucidated on the basis of chemical and spectral data.

Jasamplexosides A, B and C: Novel Dimeric and Trimeric Secoiridoid Glucosides from Jasminum amplexicaule.

Three new secoiridoid glucosides, jasamplexosides A, B and C, were isolated from the crude drug "Niu du teng", the leaves and stems of JASMINUM AMPLEXICAULE, together with the known secoiridoid glucosides, 10-hydroxyligstroside and jasminoside. Their structural elucidation by spectroscopic studies is described.

Cross-antigenicity between penams and cephems by intradermal skin test and leucocyte migration test in guinea pigs.

The delayed-type hypersensitivity (DTH) reactions for penams or cephems of beta-lactam antibiotics were investigated by intradermal skin test and leucocyte migration test (LMT) in guinea pigs. The animals were immunized with ampicillin (ABPC) or cephalexin (CEX) using Freund's complete adjuvant. The cross-reactivities among ABPC, penicillin G (PCG) and cloxacillin as penam and CEX, cephalothin (CET) and cephalosporin C (CEPC) as cephem and phenylglycine (PhGly), which is the amino acyl side chain of ABPC and CEX, were examined. By intradermal reaction, ABPC-sensitized animals showed a cross-reaction with CEX, PCG and CET, but CEX-sensitized animals did not cause cross-reaction with ABPC. The CEX-sensitized group exhibited slight cross-reactions to CET and PhGly. PhGly exhibited low immunogenicity only in maximization test of guinea pig. The above results indicate that there is the difference in cross-reactivity between penams and cephems in skin test. In LMT, all the ABPC-sensitized animals reacted with ABPC and showed cross-reactions with all drugs tested. The CEX-sensitized group reacted with 4 out of 7 animals with CEX and exhibited cross-reactivities to ABPC, PCG, CET, CEPC and PhGly. The cross-reactivity between intradermal skin reaction and LMT elicited some different results.

Purification and properties of (S)-tetrahydroprotoberberine oxidase from suspension-cultured cells of Berberis wilsoniae.

A novel oxidase, catalyzing in the presence of oxygen the removal of four hydrogen atoms from a number of tetrahydroprotoberberines with simultaneous production of 1 mol H2O2 and H2O each, has been discovered and purified to homogeneity from Berberis wilsoniae cell cultures. This enzyme, (S)-tetrahydroprotoberberine oxidase, exhibited strict specificity for the (S)-enantiomer of tetrahydroprotoberberines and 1-benzylisoquinoline alkaloids, a pH optimum at 8.9, a molecular mass of 105 kDa and consisted of two subunits each of 53 kDa and covalently bound flavin. The Km values for (S)-scoulerine and (S)-norreticuline were 25 microM and 150 microM respectively. Concentration of the end-products, either protoberberines or H2O2, greater than 0.5 mM caused severe enzyme inhibition. This catalyst was responsible for the conversion of (S)-tetrahydrocolumbamine to the key intermediate, columbamine, in the metabolic pathway leading to berberine, jatrorrhizine and palmatine.

Chemical properties of lipopolysaccharide-like substance (LLS) extracted from Leptospira interrogans serovar canicola strain Moulton.

The aqueous layer was isolated from Leptospira interrogans serovar canicola strain Moulton by the hot phenol-water method. After ultracentrifugation, the precipitate was designated as lipopolysaccharide-like substance (LLS) fraction and the chemical composition was compared with that of bacterial LPS. The LLS fraction consists of 35.2% carbohydrate, 3.8% amino sugar, 36.4% lipid, 15.2% protein, and 0.3% phosphorus. Neutral sugars were detected as rhamnose, arabinose, xylose, 4-O-methylmannose, mannose, galactose, and a small amount of erythrose, fucose and glucose by gas-liquid chromatography (GLC), but 2-keto-3-deoxyoctonic acid was not detected in the LLS by thiobarbituric acid test and high voltage paper electrophoresis. Fatty acids detected by GLC were decanoic acid (C10: 0), dodecanoic acid (C12: 0), dodecenoic acid (C12: 1), tridecenoic acid (C13: 1), tetradecanoic acid (C14: 0), hexadecanoic acid (C16: 0), hexadecenoic acid (C16: 1), and octadecenoic acid (C18: 1). With SDS-polyacrylamide gel electrophoresis, bacterial LPS showed many orderly bands, while the banding pattern of the leptospiral LLS was very simple. These findings demonstrate that the physicochemical properties and chemical composition of LLS fraction from Leptospira are different from those of LPS extracted from gram-negative bacteria such as Enterobacteriaceae, and suggesting that Leptospira has no typical LPS.

A Highly Specific O-Methyltransferase for Nororientaline Synthesis Isolated from Argemone platyceras Cell Cultures.

A highly specific new enzyme, S-adenosyl-L-methionine: (6-O-methyl-norlaudanosoline)-5'-O-methyltransferase which catalyses the formation of nor-orientaline from 6-O-methyl-norlaudanosoline and SAM was discovered, partially purified, and characterized. ARGEMONE PLATYCERAS cell suspension cultures served as enzyme source.

Partial Purification and Properties of S-Adenosylmethionine: (R), (S)-Norlaudanosoline-6-O-Methyltransferase from Argemone platyceras Cell Cultures.

A new enzyme, S-adenosylmethionine: (R), (S)-norlaudanosoline-6-O-methyltransferase, was isolated from the soluble protein extract of A. PLATYCERAS cell cultures and purified approximately 80-fold. This enzyme catalyses the formation of 6-O-methylnorlaudanosoline, and, to a minor extent, 7-O-methylnorlaudanosoline from SAM and (S), as well as (R), norlaudanosoline. The apparent molcular weight of the enzyme is 47000 Dalton. The pH-optimum of the enzyme is 7.5, the temperature optimum, 35 degrees C. Apparent K (M) values for (S) and (R)-norlaudanosoline were 0.2 mM, and for SAM, 0.05 mM. The transferase shows high substrate specificity for tetrahydrobenzylisoquinoline alkaloids. Simple orthophenols, like phenylpropane derivatives, coumarins or flavonoids, are not accepted as substrates. The enzyme is widely distributed in benzylisoquinoline-containing plant cell cultures and is present in differentiated plants like PAPAVER SOMNIFERUM.

Partial Purification and Properties of (S)-Norlaudanosoline Synthase from Eschscholtzia tenuifolia Cell Cultures.

A new enzyme, (S)-norlaudanosoline synthase, which catalyses the synthesis of (S)-norlaudanosoline from dopamine and 3,4-dihydroxyphenylacetaldehyde was isolated from the soluble protein extract of ESCHSCHOLTZIA TENUIFOLIA cell suspension cultures and purified approximately 40-fold. The apparent molecular weight of the enzyme is 15 500 Dalton. The pH optimum is 7.8, temperature optimum 40 degrees C, apparent K (M) values for dopamine and dihydroxyphenyl-acetaldehyde are 1.5 mM and 0.7 mM respectively. The synthase shows high substrate specificity in that only the phenylacetaldehydes are transformed but not the phenylpyruvates. No apparent cofactor requirement could be demonstrated. By means of isoelectric focusing and disc-gel electrophoresis evidence was obtained for the existence of four norlaudanosoline synthase isoenzymes, none of which catalyses the reaction of dopamine with 3,4-dihydroxyphenylpyruvate. These enzymes are responsible for the synthesis of (S)-norlaudanosoline, the key intermediate in the formation of isoquinoline alkaloids occurring in the plant kingdom.

Alkaloids of papaveraceous plants.

From the whole plants of Corydalis tashiroi Makino a new quaternary protoberberinium base dehydrodiscretamine chloride was isolated along with four known quaternary alkaloids by the application of droplet countercurrent chromatography (DCCC). The structure of the new base was established by spectral and chemical evidence. Eight known tertiary alkaloids were also isolated from the same plant.