Biotransformation of testosterone and testosterone heptanoate by four filamentous fungi.

The microbial transformations of testosterone and testosterone heptanoate by four fungi: Absidia griseolla var. igachii PTCC 5260, Acremonium chrysogenu PTCC 5271, Fusarium fujikuroi PTCC 5144, and Fusarium solani complex PTCC 5285 were investigated for the first time. Incubation of testosterone heptanoate with F. fujikuroi and F. solani yielded three metabolites, which were isolated and characterized as testosterone, androst-4-ene-3,17-dione, and 6ß-hydroxy testosterone. 6ß-Hydroxy testosterone was the major metabolite obtained from testosterone heptanoate biotransformation by two fungal species. A. griseolla and A. chrysogenu produced 14α-hydroxy testosterone as major metabolite, together with testosterone and 6ß-hydroxy testosterone in lower yields. The biotransformation of testosterone by F. fujikuroi and A. griseolla was also investigated in order to examine the influence of the ester group on the course of transformation. Androst-4-ene-3,17-dione was only identified in the biotransformation of testosterone by F. fujikuroi. The same product was observed in incubation of testosterone by A. griseolla, together with 14α-hydroxy testosterone in very low yield. Furthermore, time course study was also carried out in order to examine the formation of metabolites as a function of time, which was determined by HPLC. The structures of compounds were determined by their comprehensive spectroscopic analysis and comparison with literature data.

A new dihydrofuranocoumarin from Opopanax hispidus (Friv.) Griseb.

Phytochemical investigation of chloroform extract of the aerial parts of Opopanax hispidus afforded a new dihydrofuranocoumarin, 3'-isobutyryl-3'-hydroxymarmesin (1a), together with six known coumarins, oreoselon, peucedanin, officinalin, smirniorin, 4'-acetyl-3'-isobutyryl-3'-hydroxymarmesin and 3'-hydroxyprantschimgin. The structures of the compounds were determined by their comprehensive spectroscopic analysis (IR, EI-MS, (1)H NMR, (13)C NMR, HMBC, COSY, HMBC and HMQC), elemental analysis and comparison with literature data.

Immobilisation of lipase on the surface of magnetic nanoparticles and non-porous glass beads for regioselective acetylation of prednisolone.

Magnetic nanoparticles (MNPs) were prepared by co-precipitation of Fe+3/Fe+2 (2:1; molar ratio) with a mean size of 40 ± 5 nm. Scanning electron microscopy, dynamic light scattering, X-ray diffraction, vibrating sample magnetometer and thermogravimetric analysis were used to characterise the MNPs. The MNPs and also hydroxylated nonporous glass beads were similarly functionalised with the aid of glutaraldehyde to be cross-linked to lipase originated from Thermomyces lanuginosus (TLL). The yield and efficiency for immobilised lipase on the MNPs were calculated as 72 ± 2.4 and 63 ± 3.5%, whereas a yield and efficiency of 60 ± 2.1 and 55 ± 4.1%, respectively, were measured for the corresponding parameters of the immobilised enzyme on the glass beads. When the immobilised TLL was compared with its free form, Michaelis-Menten kinetics indicated an insignificant change in the Michaelis constant (Km) and a drastic decrease in the maximum substrate conversion rate (Vmax). The immobilised TLL and six other commercial lipases were then checked for regioselective acetylation of prednisolone. The highest and lowest yields of the product were observed for Novozym 435 and immobilised TLL on the glass beads, respectively. Immobilised TLL retained its bioacetylation activity of prednisolone in five successive catalytic processes.

A new abietane diterpenoid from Salvia xanthocheila Boiss.

From the chloroform extract of aerial part of Salvia xanthocheila Boiss. one new abietane diterpenoid, xantoquinone (5α,6α-dimethoxy-7,11,14-trioxoabieta-8,12-diene) and one known oleanene triterpenoid namely 1ß,3ß-dihydroxy-12-oleanene were isolated. The structure of the new terpenoid was elucidated by comprehensive spectroscopic analysis including electron ionisation-mass spectra, (1)H NMR, (13)C NMR, distortionless enchancement by polarisation transfer, H,H correlation spectroscopy, heteronuclear multiple-quantum coherence and heteronuclear multiple-bond correlation.

Chemical composition and antibacterial activity of the volatile oil from seeds of Artemisia annua L. from Iran.

The composition of essential oil of the seeds of Artemisia annua L. was analysed by GC-MS. Overall, 16 volatile components were identified on the basis of their mass spectra characteristics and retention indices representing 95.5% of the total oil. Trans-3(10)-caren-4-ol (22.3%), artemisia ketone (18.6%), 1,8-cineole (14.9%), δ-selinene (13.0%) and α-pinene (8.2%) were the major compounds. Oxygenated monoterpenes were the main compounds with 51.6% followed by sesquiterpene hydrocarbons (13.3%), monoterpene hydrocarbons (9.9%) and other compounds (8.3%). The essential oil was highly active against Escherichia coli and Enterococcus faecalis.

Biotransformation of progesterone by Absidia griseolla var. igachii and Rhizomucor pusillus.

Biotransformation of progesterone using Absidia griseolla var. igachii and Rhizomucor pusillus strains as biocatalysts were investigated. Microbial hydroxylation of progesterone by A. griseolla produced two hydroxylated pregnane-like steroids. The metabolites identified as 6ß,14α-dihydroxyprogesterone and 7α,14α-dihydroxyprogesterone. R. pusillus produced 6ß,11α-dihydroxyprogesterone with excellent yield (65.5%) and 7α,14α-dihydroxyprogesterone. These metabolites were purified by TLC followed by their identification through (1)H, (13)C NMR and other spectroscopic data.

Pyridine-functionalized MCM-41 as an efficient and recoverable catalyst for the synthesis of pyran annulated heterocyclic systems.

Pyridine-functionalized MCM-41 catalyzed reactions between tetracyanoethylene and various activated CH-acid compounds are described. These reactions afford the corresponding pyran annulated heterocyclic ring systems in high yields at room temperature within a few minutes. The work-up procedure is very simple and the products do not require further purification. The catalyst can be recycled and reused for several times without observable loss of performance.

Novel one-pot three- and pseudo-five-component reactions: synthesis of functionalized benzo[g]- and dihydropyrano[2,3-g]chromene derivatives.

A novel and efficient method has been developed for the synthesis of highly functionalized benzo[g]- and dihydropyrano[2,3-g]chromene derivatives via addition and subsequently cyclization of 2-hydroxynaphthalene-1,4-dione or 2,5-dihydroxycyclohexa-2,5-diene-1,4-dione to the condensation product of an aldehyde with malononitrile in the presence of a catalytic amount of Et(3)N in CH(3)CN at ambient temperature. The procedures are very facile. The products can be obtained with simple filtration in high yields, and no more purification is needed. These compounds are closely related to ring systems such as beta-lapachone, alpha-xiloidone, lambertellin, pyranokunthone B, and WS-5995A, which have a broad spectrum of biological activities.