Marinocyanins,cytotoxic bromo-phenazinone meroterpenoids from a marine bacterium from the streptomycete clade MAR4

Six cytotoxic and antimicrobial metabolites of a new bromo-phenazinone class, the marinocyanins A-F (1–6), were isolated together with the known bacterial metabolites 2-bromo-1-hydroxyphenazine (7), lavanducyanin (8, WS-9659A) and its chlorinated analog WS-9659B (9). These metabolites were purified by bioassay-guided fractionation of the extracts of our MAR4 marine actinomycete strains CNS-284 and CNY-960. The structures of the new compounds were determined by detailed spectroscopic methods and marinocyanin A (1) was confirmed by crystallographic methods. The marinocyanins represent the first bromo-phenazinones with an N-isoprenoid substituent in the skeleton. Marinocyanins A-F show strong to weak cytotoxicity against HCT-116 human colon carcinoma and possess modest antimicrobial activities against Staphylococcus aureus and amphotericin-resistant Candida albicans.     

A Common Conformation of Stabilized Triphenyl Phosphonium Ylidic Diesters with Bulky Alkoxy Groups

The phosphonium ylidic diesters, methyl and ethyl isopropyl and, methyl and ethyl t-butyl triphenylphosphoranylidene malonates, 1a,b and 2a,b , respectively, have the syn-anti conformation in solution, as in the crystal, and the bulkier alkoxy group is oriented towards phosphorus. The ¹ H NMR spectra show that in 1a,b , the isopropyl group is oriented towards the face of a phenyl group, consistent with π shielding in the ¹ H signals, and examination of the ¹ H coupled ¹³ C NMR spectra allows assignment of the acyl carbon signals. Computed bond lengths and angles for isolated molecules are similar to those in the crystal, and the geometry and the NMR spectra indicate extensive ylidic resonance. Estimated partial atomic charges on the ester oxygens are more negative when they are oriented towards, rather than away from, phosphorus.     

Synthesis and X-Ray Crystal Structure of an Annelated Spirophosphorane

Abstract

Reaction of the 2-azidoalcohol 1 with 2-phenyl1-1,3,2-dioxaphospholane leads to a 4:1 mixture of the pentacoordinate phosphorane 3 and the diazadiphosphetidine 4. In solution, these compounds are in equilibrium, presumably involving the not detectable iminophosphorane 2. A single X-ray analysis carried out on 3 proves the structure of this type of compound which has been postulated earlier as intermediate in the synthesis of aziridines from azidoalcohols^1,2     

Phosphoryl and Thiophosphoryl Transfer Reactions: Stereochemical Imperatives for Metaphosphate and Thiometaphosphate

Abstract

The stereochemical courses of phosphoryl transfer reactions in aprotic solvents and thiophosphoryl transfer reactions in protic solvent have been determined. The extensive racemisation observed in both instances is discussed in terms of metaphosphate and thiometaphosphate intermediates of significant life-times.     

Cationic Lanthanide Luminescent Copolymer: Design,Synthesis and Interaction with DNA

Polymerizable rare earth complex Eu(AA)₃Phen was synthesized by complexion of europium ion, acrylic acid (AA), and 1,10-phenanthroline (Phen). The structure and fluorescence properties of the complex were studied by elemental analysis, ¹H-NMR spectroscopy, and fluorescence spectroscopy. Eu-containing copolymer poly(PEGMA-co-MMA-co-METAC-co-Eu(AA)₃Phen) (PPMMEu) was then synthesized by free radical copolymerization of Eu(AA)₃Phen and other functional monomers including poly(ethylene glycol) methyl ether methacrylate (PEGMA) and [2-(Methacryloyloxy) ethyl] trimethylammonium chloride (METAC). ¹H-NMR spectroscopy and fluorescence spectroscopy were used to characterize the copolymer and the interactions between the copolymer and DNA was investigated by TEM, fluorescence spectroscopy, and agarose gel electrophoresis. The desired luminescent cationic copolymer was successfully obtained. The copolymer can form micelles in water solution and can efficiently bind to DNA molecules through electrostatic interaction. The results suggest the potential use of PPMMEu in bioprobes and gene vectors.     

Polyethynylferrocene

The completely conjugated polymer, polyethynylferrocene, was prepared by heating ethynylferrocene with catalytic amounts of azobisisobutyronitrile to 180-240[ddot] under nitrogen in bulk. Cyclotrimerization competes with polymerization under these conditions. Pure low molecular weight polyethynylferrocene was isolated and characterized by IR and NMR spectroscopy and by a gel permeation chromatography. The pure polymer exhibits a conductivity of 2 × 10^{?14 ?1} cm^?1. Attempts to prepare polyethynylferrocene by heating acetylferrocene in molten zinc chloride were, contrary to literature reports, unsuccessful. A polymer containing hydroxyl and keto groups was obtained, and extensive degradation of the ferrocene groups occurred. The general reaction scheme is discussed. It includes cleavage of cyclopentadienyl rings from ferrocene and the incorporation of cyclopentane rings into the polymer structure.     

Sodiation as a tool for enhancing the diagnostic value of MALDI‐TOF/TOF‐MS spectra of complex astaxanthin ester mixtures from Haematococcus pluvialis

The microalga Haematococcus pluvialis produces the pigment astaxanthin mainly in esterified form with a multitude of fatty acids, which results in a complex mixture of carotenol mono‐ and diesters. For rapid fingerprinting of these esters, matrix‐assisted laser desorption ionization time of flight mass spectrometry (MALDI‐TOF/TOF‐MS) might be an alternative to traditional chromatographic separation combined with MS. Investigation of ionization and fragmentation of astaxanthin mono‐ and diester palmitate standards in MALDI‐TOF/TOF‐MS showed that sodium adduct parent masses [M + Na]⁺ gave much simpler MS² spectra than radical / protonated [M]^+● / [M + H]⁺ parents. [M + Na]⁺ fragments yielded diagnostic polyene‐specific eliminations and fatty acid neutral losses, whereas [M]^+● / [M + H]⁺ fragmentation resulted in a multitude of non‐diagnostic daughters. For diesters, a benzonium fragment, formed by polyene elimination, was required for identification of the second fatty acid attached to the astaxanthin backbone. Parents were forced into [M + Na]⁺ ionization by addition of sodium acetate, and best signal‐to‐noise ratios were obtained in the 0.1 to 1.0 mM range. This method was applied to fingerprinting astaxanthin esters in a crude H. pluvialis extract. Prior to MALDI‐TOF/TOF‐MS, the extract was fractionated by normal phase Flash chromatography to obtain fractions enriched in mono‐ and diesters and to remove pheophytin a, which compromised monoester signals. All 12 types of all‐trans esterified esters found in LC were identified with MALDI‐TOF/TOF‐MS, with the exception of two minor monoesters. Copyright © 2013 John Wiley & Sons, Ltd.