Ugi-type four-component reaction for a novel synthesis of 5-oxo-perhydrofuro[3,2-b]pyran carboxylate derivatives

The four-component coupling (4CC) of sugar hydroxyaldehyde, Meldrum’s acid, isocyanide, and a secondary alcohol in dichloromethane has been accomplished at room temperature in a highly stereoselective manner to produce a novel class of carbohydrate derivatives, 5-oxo-perhydrofuro[3,2-b]pyrans in good yields with trans-selectivity. The stereochemistry of the products was assigned by various NMR experiments.     

Enzyme-mediated biodegradation of heat treated commercial polyethylene by Staphylococcal species

Extruded low-density polyethylene (LDPE) films commonly available in the market as 20-micron thick carrier bags were autoclaved, overlaid on nutrient agar plates and inoculated with BP/SU1 strain of Staphylococcus epidermis. The nutrient agar plate showed growth of the organism within two to three days. The polymer film supporting the growth of the organism showed pore formation as recorded by SEM analysis. The growth of BP/SU1 is supported by the presence of shredded LDPE as its only carbon source in inorganic salt minimal nutrient medium. The organism survives even after three months of inoculation and this is accompanied by gradual breakdown of the size of the shredded plastic as seen by light scattering. The cell-free supernatant of the organism, grown with the help of shredded plastic shows the presence of the over expressed proteins with approximate molecular weight of about 55 kDa and 35 kDa, through SDS-PAGE analysis.     

Development and validation of an LC-ESI-MS/MS method for simultaneous quantitation of olmesartan and pioglitazone in rat plasma and its pharmacokinetic application

A simple, high‐throughput and specific high‐performance liquid chromatography tandem mass spectrometry method has been developed and validated according to the FDA guidelines for simultaneous quantification of olmesartan and pioglitazone in rat plasma. The bioanalytical method consists of liquid–liquid extraction and quantitation by triple quadrupole mass spectrometry using electrospray ionization technique, operating in multiple reaction monitoring and positive ion modes. The compounds were eluted isocratically on a C₁₈ column with a mobile phase consisting of a mixture of methanol and water (containing 0.5% formic acid) in a ratio of 9:1. The response to olmesartan and pioglitazone was linear over the range 0.01–10 µg/mL. The validation results demonstrated that the method had satisfactory precision and accuracy across the calibration range. Intra‐ and inter‐day precisions ranged from 0.66 to 3.32 and from 0.94 to 2.93% (%CV), respectively. The accuracy determined at three quality control levels was within 91.27–107.28%. There was no evidence of instability of the analytes in rat plasma following the stability studies. The method proved highly reproducible and sensitive and was successfully applied in a pharmacokinetic study after single dose oral administration of olmesartan and pioglitazone to the rat. Copyright © 2010 John Wiley & Sons, Ltd.     

CONTROLLING THE 3D NANOSCALE ORGANIZATION OF BULK HETEROJUNCTION POLYMER SOLAR CELLS

In this study,the three dimensional nanoscale organization in the photoactive layers of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM) is revealed by transmission electron tomography.After annealing treatment,either at elevated temperature or during slow solvent evaporation,nanoscale interpenetrating networks are formed with high crystalline order and favorable concentration gradients of both components through the thickness of the photoactive layer.Such a tailored morphology acco...     

Palladium acetate complexes bearing chelating N-heterocyclic carbene (NHC) ligands: Synthesis and catalytic oxidative homocoupling of terminal alkynes

The imidazolium salts 1,1′-dibenzyl-3,3′-propylenediimidazolium dichloride and 1,1′-bis(1-naphthalenemethyl)-3,3′-propylenediimidazolium dichloride have been synthesized and transformed into the corresponding bis(NHC) ligands 1,1′-dibenzyl-3,3′-propylenediimidazol-2-ylidene (L₁) and 1,1′-bis(1-naphthalenemethyl)-3,3′-propylenediimidazol-2-ylidene (L₂) that have been employed to stabilize the Pd^II complexes PdCl₂(κ²-C,C-L₁) (2a) and PdCl₂(κ²-C,C-L₂) (2b). Both latter complexes together with their known homologous counterparts PdCl₂(κ²-C,C-L₃) (1a) (L₃ = 1,1′-dibenzyl-3,3′-ethylenediimidazol-2-ylidene) and PdCl₂(κ²-C,C-L₄) (1b) (L₄ = 1,1′-bis(1-naphthalenemethyl)-3,3′-ethylenediimidazol-2-ylidene) have been straightforwardly converted into the corresponding palladium acetate compounds Pd(κ¹-O-OAc)₂(κ²-C,C-L₃) (3a) (OAc = acetate), Pd(κ¹-O-OAc)₂(κ²-C,C-L₄) (3b), Pd(κ¹-O-OAc)₂(κ²-C,C-L₁) (4a), and Pd(κ¹-O-OAc)₂(κ²-C,C-L₂) (4b). In addition, the phosphanyl-NHC-modified palladium acetate complex Pd(κ¹-O-OAc)₂ (κ²-P,C-L₅) (6) (L₅ = 1-((2-diphenylphosphanyl)methylphenyl)-3-methyl-imidazol-2-ylidene) has been synthesized from corresponding palladium iodide complex PdI₂(κ²-P,C-L₅) (5). The reaction of the former complex with p-toluenesulfonic acid (p-TsOH) gave the corresponding bis-tosylate complex Pd(OTs)₂(κ²-P,C-L₅) (7). All new complexes have been characterized by multinuclear NMR spectroscopy and elemental analyses. In addition the solid-state structures of 1b·DMF, 2b·2DMF, 3a, 3b·DMF, 4a, 4b, and 6·CHCl₃·2H₂O have been determined by single crystal X-ray structure analyses. The palladium acetate complexes 3a/b, 4a/b, and 6 have been employed to catalyze the oxidative homocoupling reaction of terminal alkynes in acetonitrile chemoselectively yielding the corresponding 1,4-di-substituted 1,3-diyne in the presence of p-benzoquinone (BQ). The highest catalytic activity in the presence of BQ has been obtained with 6, while within the series of palladium-bis(NHC) complexes, 4b, featured with a n-propylene-bridge and the bulky N-1-naphthalenemethyl substituents, revealed as the most active compound. Hence, this latter precursor has been employed for analogous coupling reaction carried out in the presence of air pressure instead of BQ, yielding lower substrate conversion when compared to reaction performed in the presence of BQ. The important role of the ancillary ligand acetate in the course of the catalytic coupling reaction has been proved by variable-temperature NMR studies carried out with 6 and 7′ under catalytic reaction conditions.     

Use of allylzinc halide as a source of halide: Differential addition of nucleophiles to Ts-aziridines and aldehydes under similar reaction conditions

We have observed that the allylic zinc halide under identical reaction conditions acts in different modes for different electrophiles. For Ts-aziridines the halide part of the allylic halide has been introduced as a nucleophile and for the carbonyl compounds the simple allylation reaction occurs. To the best of our knowledge this is the first report where the allylic zinc halide is the source of halide acting as nucleophile. The main advantages of the present procedure are easy to handle, no need of inert atmosphere, mild reaction conditions, and applicability to a wide variety of substrates for aziridines and carbonyl compounds.     

Steric guided change of electron transfer mechanism in benzene

In fluorescence quenching study via electron transfer (ET), the quenching rate constant (k(q)) values generally decrease with lowering of quencher concentration, since smaller concentration of quencher always leads to a red shift in the donor-acceptor (D-A) distance in ET [M. Tachiya, S. Murata, J. Phys. Chem. 96 (1992) 8441; S. Murata, M. Tachiya, J. Phys. Chem. 100 (1996) 4064; L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A 103 (1999) 5882]. However, while doing a comparative study with different carbazole (CZ) derivatives-1,4-dicyanobenzene (DCB) systems in benzene (BZ), we observed a deviation from that normal behaviour. It was found that for all of them with lower quencher (DCB) concentration, k(q) values actually increase instead of the expected reduction. Exceptionally, for simple CZ (C12H9N) with decrease in concentration of DCB, k(q) values can even reach the order of energy transfer (10(11) s(-1)). Interestingly, it is not observed when toluene (TL) or xylene (XY) is used as solvent. To explain this unique observation, a sandwich type of molecular structure is predicted, where BZ sliding in between CZ and DCB brings them closer enough, imparting more through bond character to CZ-DCB interaction and hence a higher rate of ET (k(q)) is observed [L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A. 103 (1999) 5882].