New Oenotheralanosterol A and B Constituents from the Oenothera biennis Roots

Two new compounds oenotheralanosterol A and B along with four known compounds have been isolated from the roots of Oenothera biennis. Their structures have been elucidated with the help of 300 MHz NMR using 1D and 2D spectral methods viz: ¹H and ¹³C NMR, ¹H‐¹H COSY, ¹H‐¹³C HETCOR and DEPT aided by EIMS, ESI Mass and IR spectroscopy.     

Microwave-assisted rapid and efficient deprotection and direct esterification and silylation of MOM and EOM ethers catalyzed by [Hmim][HSO4] as a Br?nsted acidic ionic liquid

Abstract  

1-Methylimidazolium hydrogensulfate, [Hmim][HSO₄], a Br?nsted acidic room temperature ionic liquid, is used as a catalyst and reaction medium for facile and eco-friendly deprotection of methoxymethyl (MOM) and ethoxymethyl (EOM) ethers to their corresponding alcohols under thermal conditions (Δ) and microwave irradiation (MW). Furthermore, one-pot interconversion to the respective acetates and trimethylsilyl (TMS) ethers was also achieved.     

Chemical profiling and standardization of Lepidium meyenii (Maca) by reversed phase high performance liquid chromatography

Lepidium meyenii (Maca) is one of the few plants that can be cultivated in the harsh climate of the Andes. Its nutritious hypocotyl is traditionally used as food and medicine, and Maca products are increasingly becoming popular in the western world as tonics. This paper describes the first analytical method allowing the determination of the main macamides and macaenes, the marker compounds of L. meyenii. A separation within 35 min was possible by using a C-12 stationary phase, an acidic mobile phase comprising of acetonitrile and water, and raising the column temperature to 40 degrees C. By monitoring the separation at 210 and 280 nm, the markers were detectable as low as 0.40 microg/ml. In order to validate the method, accuracy, precision, linearity, limit of detection and intra/inter day repeatability were determined. The analysis of several commercially available Maca products showed a similar qualitative pattern but significant differences in the quantitative composition. The percentage of total markers in the preparations varied from 0.15 to 0.84%, resulting in daily intakes for the consumer from 1.52 to 14.88 mg, respectively.     

Enzyme inhibiting lignans from Vitex negundo

Two new lignans trivially named negundins A (1) and B (2), were isolated along with (+)-diasyringaresinol (3), (+)-lyoniresinol (4), vitrofolal E (5) and vitrofolal F (6), reported for the first time from this species. The structures of the new compounds were established through spectral studies. Compound 2 showed potent inhibitory activity against lipoxygenase enzyme, while 5 showed moderate activity against butyryl-cholinesterase.     

Novel poly(amide-imide)s from 2,6-bis(5-amino-1-naphthoxy) pyridine

Reaction of 5-amino-1-naphthol with 2,6-dichloropyridine resulted in preparation of 2,6-bis(5-amino-1-naphthoxy) pyridine (AN). This pyridine-based ether diamine was reacted with two moles of trimellitic anhydride (TMA) to synthesize related diimide-diacid (DIDA). Direct polycondensation reaction of DIDA with different diamines in the presence of triphenyl phosphite (TPP) afforded seven different poly(amide-imide)s. All the polymers were characterized and their physical and thermal properties were studied. The inherent viscosity of the polymers was about 0.44-0.50 dl g⁻¹ and they showed high thermal stability.     

Triterpenoid saponin from the bark of Guaiacum officinale L

A new triterpenoid saponin, guaianin R (1) was isolated from the n-BuOH extract of bark of Guaiacum officinale L. It was characterized as akebonic acid-3-O-[alpha-L-rhamnopyranosyl-(1 --> 3)-beta-D-glucopyranosyl-(1 --> 3)-alpha-L-rhamnopyranosyl-(1 --> 2)-alpha-L-arabinopyranoside]-28-O-[beta-D-glucopyranosyl]-ester. The structure was established with the help of a comparative study of 1D and 2D 1H- 13C NMR methods. A number of other saponins were isolated and reported from the same species.     

Efficient and Selective Conversion of Trimethylsilyl and Tetrahydropyranyl Ethers to their Corresponding Acetates and Benzoates Catalyzed by Bismuth(III) Salts

 A variety of TMS and THP ethers are efficiently converted to their corresponding acetates and benzoates with acetic and benzoic anhydrides in the presence of catalytic amounts of Bi(III) salts such as BiCl₃, Bi(TFA)₃, and Bi(OTf)₃. The present method is also effective for the selective acetylation and benzoylation of TMS and THP ethers of alcohols in the presence of phenolic ethers.     

Liquid chromatography-tandem mass spectroscopic method for the determination of zerumbone in human plasma and its application to pharmacokinetics

A rapid, sensitive, specific and selective LC-MS/MS method for the determination of zerumbone (ZER) in human plasma using 2,4-diamino-6-(4-methoxyphenyl)-1,3,5-triazine (DMTZ) as an internal standard (IS) has been developed and validated. ZER was chromatographed on C8 column using a mobile phase of acetonitrile/water (80:20, v/v) at a flow rate of 0.25 ml min(-1) . Quantitation was achieved using ESI+ interface, employing multiple reaction monitoring (MRM) mode at m/z 219 > 81 and 218 > 134 for ZER and IS, respectively. The calibration standards were linear over a range of 5-3000 ng ml(-1) (r(2)=0.9994) with an LLOQ of 5 ng ml(-1) (RSD %; 11.4% and bias%; 9.5%). Intra- and inter-day precision of ZER assay ranged from 0.18 to 3.56% with accuracy (bias) that varied between -5.09 and 4.3%, demonstrating good precision and accuracy. Recoveries of ZER and the IS from human plasma were above 85%. The developed method was validated for the determination of ZER in rat plasma. Linearity, stability of ZER and the ME on rat plasma were discussed. The applicability of the developed method was demonstrated by measuring ZER in rat plasma samples following intravenous and intraperitoneal administration of ZER prepared in hydroxypropyl-β-cyclodextrin (HPβCD) and sodium carboxymethyl cellulose (CMC), respectively, in 20 mg kg(-1) and this study indicated a clear significant difference (p<0.05) in pharmacokinetic parameters of ZER in ZER/HPβCD complex compared with ZER in CMC preparation.     

Solubilization of triphenylamine, triphenylphosphine, triphenylphosphineoxide and triphenylmethanol in single and binary surfactant systems

Solubilization and co-solubilization of triphenyls (TPs) viz., triphenylphosphine (TPP), triphenylphosphineoxide (TPPO), triphenylamine (TPA) and triphenylmethanol (TPM) were studied in various single and binary surfactant systems at 25 °C using UV-visible spectroscopy and HPLC. The solubilization capacities of different micelles towards TPs were found to be a function of the nature and structure of solubilizates, locus of solubilization, size of micelles and the nature of interactions between the solubilizate and micelles. The effect of surfactant mixing on the solubilization of TPs was evaluated using the Regular Solution Approach (RSA). The solubility enhancement of TPs within mixed micelles relative to that observed in single surfactant systems was explained in light of the structural micellar changes associated with the mixing of ionic and non-ionic surfactants. Moreover, kinetics of oxidation of TPP by hydrogen peroxide investigated in these surfactant systems was found to be sensitive to the nature of micelle and the locus of solubilization of TPP within the micelles.     

Application of factorial design and Box-Behnken matrix in the optimisation of a microwave-assisted extraction of essential oils from Salvia mirzayanii

Essential oil of Salvia mirzayanii cultivated in Iran was obtained by microwave assisted extraction (MAE) procedures. The essential oil was analysed by capillary gas chromatography using flame ionisation and mass spectrometric detections. The effects of different parameters, such as microwave power, temperature, time and type of solvent on the MAE of Salvia mirzayanii oil were investigated. Results of the two-level fractional factorial design (2(4-1)) based on an analysis of variance demonstrated that only the power, temperature and type of solvent were statistically significant. Optimal conditions for the extraction of essential oils were obtained by using Box-Behnken design. For optimum recovery of essential oil the variables power, temperature and solvent values were 115?W, 50°C and 14?s, respectively. Under the optimised experimental conditions, the extraction yield of microwave assisted extraction was 11.2% (w/w).