Sesquiterpene lactone glucosides and alkyl glycosides from the fruit of cumin

From the polar portion of the methanolic extract of cumin (fruit of Cuminum cyminum L.), two sesquiterpenoid glucosides, cuminoside A and B, and two alkyl glycosides were isolated together with five known compounds. Their structures were established as (1S,5S,6S,10S)-10-hydroxyguaia-3,7(11)-dien-12,6-olide beta-D-glucopyranoside, (1R,5R,6S,7S,9S,10R,11R)-1,9-dihydroxyeudesm-3-en-12,6-olide 9-O-beta-D-glucopyranoside, methyl beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside and ethane-1,2-diol 1-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside, respectively.     

Glycosides of 2-C-methyl-D-erythritol from the fruits of anise,coriander and cumin

Eight glycosides of 2-C-methyl-D-erythritol (1) were isolated from the fruit of anise, and their structures were clarified as 1-O-beta-D-glucopyranoside, 3-O-beta-D-glucopyranoside, 4-O-beta-D-glucopyranoside, 1-O-beta-D-fructofuranoside, 3-O-beta-D-fructofuranoside, 4-O-beta-D-fructofuranoside, 1-O-beta-D-(6-O-4-hydroxybenzoyl)-glucopyranoside and 1-O-beta-D-(6-O-4-methoxybenzoyl)-glucopyranoside of 2-C-methyl-D-erythritol (2-9), respectively. Furthermore, 2 and 4 were isolated from the fruit of coriander, and 2, 3 and 4 were isolated from the fruit of cumin. Though the phosphate of 1 was known to be one of the first precursors of isoprenoids in the non-mevalonate pathway, and 1 is considered to be a common constituent in Umbelliferous plants, the glycosides of 1 are found for the first time.     

Improvement of phenylethanoid glycosides production by a fungal elicitor in cell suspension culture of Cistanche deserticola

When, on the 15th day of growth, an elicitor from Fusarium solani was added at 40 mg l^–1 to Cistanche deserticola cell suspension cultures, the contents of echinacoside, acteoside and total phenylethanoid glycosides (PeGs) in cultured cells all increased over the next 27 d by over 100% to 15 mg g^–1 dry wt, 9 mg g^–1 dry wt and 57 mg g^–1 dry wt, respectively. The final biomass (1.3 mg dry wt ml^–1) was not affected.     

Discriminative determination of alkyl methylphosphonates and methylphosphonate in blood plasma and urine by gas chromatography-mass spectrometry after tert.-butyldimethylsilylation

A method for determining two nerve gas hydrolysis products, alkyl (ethyl, isopropyl and pinacolyl) methylphosphonates (RMPAs) and methylphosphonate (MPA), separately, in human plasma and urine samples was developed, using two different deproteinization procedures. In the first method, the plasma sample was deproteinized by adding a fourfold volume of acetonitrile, followed by passing the supernatant through a Bond Elut strong anion-exchange (SAX) cartridge [fluoride (F(-)) form]. After washing the cartridge with water and methanol, the RMPAs were eluted with a 3% (v/v) solution of methanolic ammonia, and analyzed by gas chromatography-mass spectrometry (GC-MS) after tert.-butyldimethylsilyl (TBDMS) derivatization. The detection yields of TBDMS derivatives of RMPAs were in the range of 69 to 99%, in contrast to the poor yields obtained when only acetonitrile deproteinization pretreatment was used (yield: 13-26%). The yield of the TBDMS derivative of MPA was very low (8%), however. In a the second method, a plasma sample was deproteinized by adding a half volume of 10% (w/v) trichloroacetic acid (TCA), and the resulting supernatant was extracted with diethyl ether to remove TCA, the aqueous fraction was then passed through a Bond Elut SAX cartridge. After washing the cartridge with 0.5% (v/v) methanolic ammonia, MPA was eluted with 3% (v/v) methanolic ammonia. The detection yield of the TBDMS derivative of MPA was nearly quantitative. A pretreatment method using SAX solid-phase extraction was also developed for the cleanup of a urine sample, in which the sample was directly applied to a Bond Elut SAX cartridge, followed by elution of the RMPAs and MPA with 3% (v/v) methanolic ammonia, which were then derivatized and analyzed by GC-MS. The detection yields of TBDMS derivatives of RMPAs and MPA were in the range of 61 to 97%.     

Mechanism of action of oritavancin and related glycopeptide antibiotics

Oritavancin (LY333328) is a semisynthetic glycopeptide antibiotic having excellent bactericidal activity against glycopeptide-susceptible and -resistant Gram-positive bacteria. Oritavancin is the N-alkyl-p-chlorophenylbenzyl derivative of chloroeremomycin (LY264826) and is currently in phase III clinical trials for use in Gram-positive infections. Studies show that oritavancin and related alkyl glycopeptides inhibit bacterial cell wall formation by blocking the transglycosylation step in peptidoglycan biosynthesis in a substrate-dependent manner. As with other glycopeptide antibiotics, including vancomycin, the effects of oritavancin on cell wall synthesis are attributable to interactions with dipeptidyl residues of peptidoglycan precursors. Unlike vancomycin, however, oritavancin is strongly dimerized and can anchor to the cytoplasmic membrane, the latter facilitated by its alkyl side chain. Cooperative interactions derived from dimerization and membrane anchoring in situ can be of sufficient strength to enable binding to either dipeptidyl or didepsipeptidyl peptidoglycan residues of vancomycin-susceptible and -resistant enterococci, respectively. This review describes the antibacterial activity of oritavancin, and examines the evidence supporting the proposed mechanism of action for this agent and related analogs.     

Palladium (II)-catalyzed alternating copolymerization of alkenes with sulfur dioxide

Cationic palladium(II) complexes of the type [L₂Pd(CH₃)(CH₃CN)]BF₄ (L₂ = 1,3-bis(diphenylphosphino)propane (Dppp) or 1,2-bis(2,5-dimethylphospholano)benzene (Me-Duphos)) were found to catalyze the alternating copolymerization of ethene, propene and cyclopentene with sulfur dioxide, as well as the terpolymerization of ethene, propene and sulfur dioxide. The resultant materials are high melting solids with an alternating alkene-SO₂ structure and an exclusive head-to-tail enchainment for propene.     

Titanium-carbon functionalities on an oxo surface defined by a calix [4] arene moiety and its redox chemistry

Lithiation of [p-Bu^t-calix[4]-(OMe)₂(OH)₂] (1), followed by reaction with TiCl₃(thf)₃ or TiCl₄(thf)₂, led to the corresponding titanium-calix[4]arene complexes [p-Bu^t-calix[4]-(OMe)₂(O)₂]TiCl] (2) and [p-Bu^t-calix[4]-(OMe)₂(O)₂]TiCl₂] (3), respectively. Reaction of 1 with TiCl₄(thf)₂ results in demethylation of the calix[4]arene and the obtention of [p-Bu^t-calix[4]-(OMe)₂(O)₃]TiCl] (4), whose hydrolysis led to [p-Bu^t-calix[4]-(OMe)(OH)₃] (6). The preparation of 6 can be carried out as a one-pot synthesis. Both 2 and 4 undergo alkylation reactions using conventional procedures, thus forming surprisingly stable organometallic species, namely [p-Bu^t-calix[4]-(OMe)₂(O)₂Ti(R)] (R = Me (7); CH₂Ph (8), p-MeC₆H₄ (9) and [p-Bu^t-calix[4]-(OMe)(O)₃Ti(R)] (R = Me (10); CH₂Ph (11); p-MeC₆H₄ (12)). Complexes 7 and 9 undergo a thermal oxidative conversion into 10 and 12, occurring with the demethylation of one of the methoxy groups. A solid state structural property of 9 and 12 has been revealed by X-ray analysis showing a self-assembly of the monomeric units into a columnar polymer, where the p-tolyl substituent at the metal functions as a guest group for an adjacent titanium-calixarene. Reductive alkylation of 3 with Mg(CH₂Ph)₂ gave 8 instead of forming the corresponding dialkyl derivative. Two synthetic routes have been devised for the synthesis of the Ti(III)-Ti(III) dimer [p-Bu^t-calix[4]-(OMe)(O)₃Ti]₂] (13): the reduction of 4 and the reaction of TiCl₃(thf)₃ with the lithiated form of 6. A very strong antiferromagnetic coupling is responsible for the peculiar magnetic behavior of 13. The proposed structures have been supported by the X-ray analyses of 4, 9, 12 and 13.     

Rhododendrol biosynthesis and metabolism in Acer nikoense callus

Cell suspensions derived from Acer nikoense callus, not containing (S)-rhododendrol, converted 4-(p-hydroxyphenyl)-2- butanone into (R)-, (S)-rhododendrol and their glycosides. (R)- and (S)-rhododendrol formed was only detected in the culture medium and their glycosides only in the cells. The former compound disappeared within a short time and the latter one also tended to decrease during prolonged culture. Quantitative analysis of rhododendrol glycosides in the callus showed that most of them were (S)-rhododendrol 2-O--D-glucopyranoside and its content was much lower than that of the original plants. © Rapid Science Ltd. 1998     

Sorption isotherms and kinetics in the primary biodegradation of anionic surfactants by immobilized bacteria: I. Pseudomonas C12B

The surfactant-degrading biocatalyst Pseudomonas C12B was immobilized by covalent linking on silanized inorganic supports and by physical entrapment of cells within reticulated polyurethane foam. Both immobilized biocatalysts have been shown to be appropriate for the effective primary biodegradation of the anionic surfactants sodium dodecyl sulphate (SDS), dodecylbenzene sulphonic acid (DBS), dioctyl sulphosuccinate (DOSS) and dihexyl sulphosuccinate (DHSS). The overall surfactant removal from water by cells entrapped in reticulated polyurethane foam exhibits a biphasic process, a rapid sorption step of the surfactant onto the cell-loaded support and the intrinsic primary biodegradation slower step, both acting cooperatively. The optimization of variables for the adsorption and the biodegradation processes (flow rate, particle size, substrate concentration) have been studied. Sorption isotherms for the surfactants on reticulated polyurethane foam have been established as type II of the Brunauer, Deming, Deming and Teller (BDDT) classification. The kinetics of the primary biodegradation of SDS by cells covalent linked on sepiolite treated with 3-aminopropyl triethoxysilane (APTS) were found to be first-order. In this case, surfactant adsorption does not exist.