Dammarane triterpenes of Commiphora confusa resin

Fractionation of a steam distilled residue of Commiphora confusa resin has yielded four novel dammarane triterpenes characterised as (20S)-3beta-acetoxy-12beta,16beta-trihydroxydammar-24-ene, (20S)-12beta,16beta-trihydroxydammar-24-ene-3beta-O-beta-glucopyranoside, (20S)-3beta-acetoxy-12beta,16beta,25-tetrahydroxydammar-23-ene, and (20S)-3beta,12beta,16beta,25-pentahydroxydammar-23-ene. The known compounds beta-amyrin, 3beta-amyrinacetate, 2-methoxyfuranodienone, 2-acetoxyfuranodienone, (20R)-3beta-acetoxy-16beta-dihydroxydammar-24-ene, (20R)-3beta,16beta-trihydroxydammar-24-ene, 3beta-acetoxy-16beta-hydroxydammar-24-ene, 3beta-hydroxydammar-24-ene, 3beta-acetoxydammar-24-ene, and beta-sistosterol were also isolated from the same extract. The structures of the compounds were determined using spectroscopic, physical, and chemical methods.     

Formation of fluorinated nonionic surfactant microemulsions in hydrofluorocarbon 134a (HFC 134a)

A structurally related series of fluorinated nonionic oxyethylene glycol surfactants of the type C(m)F(2m+1)(CH(2))(n)O[(CH(2)CH(2)O)(p)H], denoted C(m.n)E(p) (where m=4, 6, or 7, m=1 or 2, and p=4 or 6) were synthesized and their surface behavior in aqueous solution was characterized. The ability of these surfactants to form water-in-hydrofluorocarbon (HFC) propellant 134a microemulsions suitable for use in the aerosolized delivery of water-soluble drugs has been investigated. Phase studies showed that, regardless of the composition used, clear one-phase systems could not be prepared if a fluorinated nonionic surfactant was used alone, or in combination with a short or medium fluorocarbon alcohol cosurfactant. Clear one-phase systems could, however, be prepared if a short-chain hydrocarbon alcohol, such as ethanol, n-propanol, or n-pentanol, was used as cosurfactant, with the extent of the one-phase region increasing with decreased chain length of the alcohol cosurfactant. Light-scattering studies on a number of the hydrocarbon-alcoholcontaining systems in the propellant-rich part of the phase diagram showed that only systems prepared with C(4.2)E(6) and propanol contained microemulsion droplets (all other systems investigated were considered to be cosolvent systems).     

Reversal of Clar's Aromatic-Sextet Rule in Ultrashort Single-End-Capped [5,5] Carbon Nanotubes

The three-fold HOMO-LUMO gap oscillation, typical of finite length armchair carbon nanotubes (CNT), has a major effect on the magnetic response of ultrashort, single-end-capped [5,5] carbon nanotubes to a perturbing magnetic field parallel to the main symmetry axis. For the CNT's containing 40, 70, and 100 carbon atoms, for which 100 % of the C=C double bonds can be grouped into aromatic-sextets, i. e., fully or complete Clar networks, large paratropic (antiaromatic) global circulations around the cylindrical axis are predicted at the DFT level of calculation. Local and semi-global diatropic (aromatic) currents of strengths not larger than that of the benzene molecule are determined for a perpendicular perturbing magnetic field. CNTs of intermediate lengths do not display this enhanced antiaromatic response. The paratropic current flow clearly shows that these complete Clar networks can be viewed as stacked cycloparaphenylene belts, each providing a double annulene circuit as a consequence of the quinoidal resonance structure that results from their closure. Paradoxically, the fully aromatic Clar structure itself is responsible for the enhanced global antiaromaticity.     

Highly selective entry to the azadirachtin skeleton via a Claisen rearrangement/radical cyclization sequence

[formula: see text] A highly diastereoselective, microwave-induced Claisen rearrangement of an appropriately substituted propargylic enol ether allows the formation of the sterically congested C8-C14 bond of azadirachtin. When combined with a radical-mediated cyclization of the corresponding allene, this sequence offers rapid entry to the framework of azadirachtin.     

Comparison of liquid chromatography/mass spectrometry, ELISA, and phosphatase assay for the determination of microcystins in blue-green algae products

More than 100 samples of blue-green algae products (consisting of Aphanizomenon, Spirulina, and unidentified blue-green algae) in the form of pills, capsules, and powders were collected from retail outlets from across Canada. The samples were extracted with 75% methanol in water and centrifuged to remove solids. Aliquots of the extracts along with spiked blank sample extracts were sent to each participating laboratory and independently analyzed for microcystins by enzyme-linked immunosorbent assay (ELISA), protein phosphatase inhibition assay, and by liquid chromatography-tandem mass spectrometry (LC-MS/MS) after sample cleanup using C18 solid-phase extraction. The results obtained by ELISA and LC-MS/MS agreed very well over a concentration range of about 0.5-35 microg/g. The colorimetric phosphatase results generally agreed with the other 2 methods. While the 2 biochemical assays measured total microcystin content compared with a standard of microcystin LR, the LC-MS/MS method measured specific microcystins (LA, LR, RR, YR) using external standards of these for identification and quantitation. Microcystin LR was found in all positive samples by LC-MS/MS. Microcystin LA was the only other microcystin found in the samples analyzed. These 2 microcystins represent essentially all the microcystins that were present in the extracts. Otherwise, the LC-MS/MS results would have been significantly lower than the results of the biochemical assays had other unknown microcystins been present.     

Photochemical deuterium exchange of the m-methyl group of 3-methylbenzophenone and 3-methylacetophenone in acidic D2O

Photolysis of the title compounds in acidic aqueous solution results in "activation" of the distal m-methyl group, resulting in deuterium exchange (Phi approximately 0.1) when D(2)O is used. The reaction is not observed in neutral aqueous solution or in deuterated organic solvents such as CD(3)CN. The reaction is best rationalized by a mechanism involving initial protonation at the carbonyl oxygen of the triplet excited state. [reaction: see text]     

Fluorinated ionic surfactant microemulsions in hydrofluorocarbon 134a (HFC 134a)

The factors influencing the formation of water-in-134a-propellant microemulsions using the fluorinated ionic surfactants ammonium perfluorooctanoate, ammonium perfluoroheptanoate, and sodium perfluorooctanoate has been determined. None of the fluorinated ionic surfactants could be used to prepare clear, one-phase systems when used as sole surfactant, but they could be when combined with a short-chain fluoro- or hydrocarbon alcohol in surfactant:cosurfactant weight-mixing ratios (K(m)) in the range 1:2 to 2:1. When hydrocarbon alcohols were used this clear region extended over a wide range of compositions and was confirmed by means of photon correlation spectroscopy (PCS) to contain microemulsion droplets in the propellant-rich part of the phase diagram. PCS studies performed in the presence of the water-soluble drug terbutaline sulfate showed that it was possible to solubilize the drug within water-in-propellant microemulsion droplets. These studies confirm for the first time that it is possible to prepare water-in-propellant 134a microemulsions using fluorinated ionic surfactants and to solubilize water-soluble drugs within these systems.     

The Solubility of the Chloromethanes in Water

Summary.  There are more than 150 papers that report on the solubility of the four chloromethanes in water. Volume 62 of the Solubility Data Series compiles and evaluates the papers concerned with the liquid–liquid solubility of the chloromethanes with water. A similar evaluation has not been carried out for the vapor–liquid solubility at a partial pressure up to the saturation vapor pressure of the four chloromethanes. This paper uses the liquid–liquid evaluated solubility values to calculate vapor–liquid Henry’s constants. They are compared with a compilation of Henry’s constants with good agreements between the calculated constants and the median of the compiled constants. It is believed that the calculated constants are a reliable set of values to use for the vapor–liquid solubility of the chloromethanes in water. E-mail: hlclever@worldnet.att.net Received October 11, 2002; accepted October 22, 2002 Published online April 24, 2003 RID="a" ID="a" Dedicated to Prof. Dr. Heinz Gamsj?ger on the occasion of his 70^th birthday     

Quantum hair and quantum gravity

A black hole may carry quantum numbers that arenot associated with massless gauge fields, contrary to the spirit of the no-hair theorems. The quantum hair is invisible in the classical limit, but measurable via quantum interference experiments. Quantum hair alters the temperature of the radiation emitted by a black hole. It also induces non-zero expectation values for fields outside the event horizon; these expectation values are non-perturbative in , and decay exponentially far from the hole. The existence of quantum hair demonstrates that a black hole can have an intricate quantum-mechanical structure that is completely missed by standard semiclassical theory.Based on an essay which received second award from the Gravity Research Foundation, 1991     

Studies on the mechanism of 1,2-dihydropyrazin-2-one ring formation from dipeptidyl chloromethyl ketone and its chemical properties: immediate deamination during catalytic hydrogenation

1,2-Dihydropyrazin-2-one derivatives, which have two aminoalkyl groups at the positions 3 and 6, were found to be efficient tools for the construction of potent, selective and long-acting opioid mimetics. During the course of preparation, we found that the catalytic hydrogenation of 3,6-bis(benzyloxycarbonylaminomethyl)-5-methyl-1,2-dihydropyrazin-2-one to remove the benzyloxycarbonyl groups resulted in a side reaction. By MS and NMR studies and by preparation of additional 1,2-dihydropyrazin-2-one derivatives, the structure of the by-product was identified as 3-aminomethyl-5,6-dimethyl-1,2-dihydropyrazin-2-one. Preparation of additional compounds substituted with deuterium provided us with sufficient information to confirm the structure of the product and to support a cyclization mechanism in its formation.