Simultaneous detection of monohydroxybenzo[a]pyrene positional isomers by reversed-phase liquid chromatography coupled to electrospray ionization mass spectrometry

A liquid chromatographic (LC) method has been developed for the separation of 11 monohydroxybenzo[a]pyrenes (OH BaPs) positional isomers, and for their detection using electrospray ionization mass spectrometry (ESI-MS). All OH BaPs isomers were separated on an octadecylsilyl (C(18))-bonded amorphous organosilica column utilizing gradient elution with acetonitrile-water and triethylamine (TEA) at pH 11.0 and determined by MS, except 2- and 8-OH BaPs which were coeluted. The lower detection limits were in the range from 1.6 micro g/L for 12-OH BaP to 12 micro g/L for 5-OH BaP without any sample enrichment. The relative standard deviations of area response were in the range from 1.8% (9-OH BaP) to 4.9% (12-OH BaP) except for 9.4% (7-OH BaP). The developed method was successfully applied to incubation mixtures of BaP and CYP1A1/epoxide hydrolase. This method identified 1-, 3- and 9-OH BaPs as the major metabolites, and 2- (and/or 8-) and 12-OH BaPs as the minor metabolites in the incubation mixture.     

Highly enantioselective synthesis of chiral 3-substituted indolines by catalytic asymmetric hydrogenation of indoles

[reaction: see text] N-Tosyl 3-substituted indoles were hydrogenated with high enantioselectivities (95-98% ee) by use of a trans-chelating chiral bisphosphine, (S,S)-(R,R)-PhTRAP ligand. The chiral catalyst, which was generated in situ from [Rh(nbd)(2)]SbF(6), PhTRAP, and Cs(2)CO(3), is useful for enantioselectively synthesizing a range of diverse optically active indolines possessing a chiral carbon at the 3-position.     

Total synthesis of scytophycin C. 1. Stereoselective syntheses of the C(1)-C(18) segment and the C(19)-C(31) segment

[structure: see text] Stereoselective total synthesis of scytophycin C, a marine 22-membered macrolide displaying potent activity against a variety of human carcinoma cell lines, has been reported in which the polypropionate structure bearing contiguous asymmetric centers was stereospecifically constructed by using new acyclic stereocontrol. This paper describes stereoselective syntheses of the C(1)-C(18) segment (Segment A) including a trans-disubstituted dihydropyran ring and the C(19)-C(31) segment (Segment B) having eight stereogenic centers.     

Volume phase transition of methacryloyl‐L‐alanine copolymer hydrogels controlled by the terminal groups in the side chains

The volume phase transition of nonionic hydrogels was controlled with a very small amount of variation (pinpoint variation) of the side chains far from the main chain. The copolymer hydrogels poly(methacryloyl‐alanine methyl ester‐co‐methacryloyl‐alanine ethyl ester) [poly(MA‐Ala‐OMe‐co‐MA‐Ala‐OEt)] and poly(methacryloyl‐alanine alkylamide‐co‐methacryloyl‐alanine ethyl ester) [poly(MA‐Ala‐NR₂‐co‐MA‐Ala‐OEt)] were studied to investigate how pinpoint variation controls the volume phase transition. All copolymer hydrogels showed a volume phase transition from a swollen phase to a collapsed phase at a definite MA‐Ala‐OEt content at a specific temperature. The MA‐Ala‐OEt content at the midpoint of the transition linearly decreased with elevation of the temperature, and the decrease was larger for poly(MA‐Ala‐OMe‐co‐MA‐Ala‐OEt) than for poly(MA‐Ala‐NR₂‐co‐MA‐Ala‐OEt). These results suggest that the association of the side chains controlling the swelling character of the hydrogels depends on the interacting ester–ester or ester–amide groups, and the former is larger than the latter. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 56–62, 2001     

Abilities of 2‐arylmethyloxy‐6‐cyanonaphthalene derivatives to initiate radical and cationic photopolymerizations

An investigation was undertaken to shed much light on the bond‐cleavage mode (heterolysis vs homolysis) of bichromophoric photoinitiators in styrene (St) and 1,2‐epoxycyclohexane (EpC) and then to develop a highly efficient hybrid‐type photoinitiator. Excited‐state 2‐(9‐anthrylmethyloxy)‐6‐cyanonaphthalene in toluene and 1,2‐dimethoxyethane, which were used instead of St and EpC, respectively, underwent both homolytic Ar? OCH₂ bond cleavage and heterolytic ArO? CH₂ bond cleavage to give the corresponding radical‐pair and ion‐pair intermediates. The charge‐separated state characteristic of the naphthol chromophore in the singlet excited state was found to play a pivotal role in this heterolytic bond‐cleavage mode. An inspection of the radical (St) and cationic (EpC) photopolymerization behavior observed in the presence of some 2‐arylmethyloxy‐6‐cyanonaphthalenes led us to conclude that the aforementioned 9‐anthrylmethyloxy‐substituted naphthalene derivative is a candidate for a functional hybrid‐type photoinitiator containing no halogen and/or metal. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 25–31, 2006     

Hydrogen bonding of aromatic amines in hydroxylic solvents 2. Absorption and emission spectroscopy of substituted 7-aminocoumarins and 7-aminocarbostyrils

The absorption and fluorescence spectra of 7-aminocoumarins and 7-aminocarbostyrils with different degrees of alkylation were studied in 2-propanol (IP), polyfluorinated alcohols and water. The spectral properties of substituted 7-aminocoumarins and 7-aminocarbostyrils in hexafluoro-2-propanol (HFP) are very different from those in 2-propanol due to the strong hydrogen-bonding (HB) interaction between the solute and the solvent (HFP). The spectral behaviour can be explained in terms of the strength of the HB interaction which depends on the degree of alkylation of the amino group and the electron affinity of the electron-accepting moiety. The absorption spectra indicate that a structural change at the amino nitrogen is induced on formation of strong hydrogen bonds.     

A practical synthesis of (−)-kazusamycin A (revised)

We describe herein a stereo-controlled and practical synthesis of three key building blocks, namely Segment AB′, Segment D, and Segment E′ needed for the total synthesis of (−)-kazusamycin A.     

Mimocin,a new isoquinolinequinone antibiotic

A new isoquinolinequinone antibiotic, mimocin(2), has been isolated from the strain of Streptomyces lavendulae. The structure of mimocin has been deduced from mass and PMR spectral data and confirmed by its synthesis.