The charge delocalised beta,beta-carotene dication--preparation, structure elucidation by NMR and reactions with nucleophiles

The reaction between beta,beta-carotene and BF3-etherates has been investigated, leading to structural elucidation of the blue product, formed in appropriate organic solvents, as a symmetrical charge delocalised dication (lambda(max) 985 nm at room temperature in CHCl3) with considerable stability. The reaction, monitored by EPR studies at -25 degrees C, occurred via free radical intermediates. A C40H56BF3 intermediate was captured by EIMS. The detailed structure of the dication was established by COSY, HSQC, HMBC and 1D and 2D ROESY NMR techniques (600 MHz, CDCl3, -20 degrees C) leading to complete assignments of 1H and 13C chemical shifts and 3J(H,H) coupling constants. The effects of the two delocalised charges on chemical shift (charge distribution) and bond distance (3J(H,H)) were considered. The results are consistent with charge delocalisation mainly in the C-5-C-9 and C-5'-C-9' regions and with bond inversion to retro shifted double bonds in the central C-13-C-13' region. A convention for denoting the charge delocalisation and bond types is presented. The experimental results are discussed relative to previous theoretical calculations of the beta,beta-carotene dication structure. (All-E) and (15-Z)-beta,beta-carotene provided the same dication. The NIR spectra and stability of dications prepared in the same manner from the related carotenes 20,20'-dinor-beta,beta-carotene, heptapreno-beta,beta-carotene and nonapreno-beta,beta-carotene were examined for comparison. Reactions of the beta,beta-carotene dication with selected nucleophiles provided products including isocryptoxanthin, isocarotene and mutatochrome with H2O as nucleophile, and isocryptoxanthin methyl ether, 8-methoxy-7,8-dihydro-beta,beta-carotene and isocarotene with CH3ONa as nucleophile. The formation of these products is rationalised from the structure assigned to the dication.     

Analysis of 'ARN' naphthenic acids by high temperature gas chromatography and high performance liquid chromatography

Examination by high temperature GC (HTGC) of the methyl esters of the so-called 'ARN' naphthenic acids from crude oils of North Sea UK, Norwegian Sea and West African oilfields revealed the distributions of resolved 4-8 ring C80 tetra acids and trace amounts of other acids. Whilst all three oils contained apparently the same major acids, the proportions of each differed, possibly reflecting the growth temperatures of the archaebacteria from which the acids are assumed to have originated. The structures of the 4, 5, 7 and 8 ring acids are tentatively assigned by comparison with the known 6 ring acid and related natural products and an HPLC method for the isolation of the individual acids is described. ESI-MS of individual acids isolated by preparative HPLC established the elution order of the 4-8 ring acids on the HPLC and HTGC systems and revealed the presence of previously unreported acids tentatively identified as C81 and C82 7 and 8 ring analogues.     

Search for narrow resonances in e+e− annihilation at petra

We have performed a search for narrow resonances in the center of mass energy range from 29.90 to 31.46 GeV using the e⁺e^? storage ring PETRA at DESY. We present the total cross section for hadron production and an upper limit for resonance production, indicating that no bound state of charge-$\text{2}\text{3}$ quarks exists in this energy range.     

Nuclear magnetic resonance spectroscopy of petroporphyrins : Self-aggregation effects, nuclear overhauser enhancements, and spin-lattice relaxation used in structural elucidation

The substitution pattern of the two major petroporphyrins of Marl Slate, the ETIO III and the C₃₂ DPEP, is determined by NMR spectroscopy alone, using self-aggregation effects, nuclear Overhauser enhancements and spin-lattice relaxation times. Protoporphyrin IX dimethyl ester was used as a model compound.     

Multiplicity distributions in e+e− annihilations at petra energies

Measurements of the charged multiplicities for hadron production in e⁺e^? annihilation in the center of mass energy range 9–32 GeV have been made. The average charged multiplicity has an energy dependence much stronger than ln s and similar to that reported for pp collisions. Quantitative differences are observed in the magnitude of both the average multiplicity 〈n_ch〉 and the dispersion D_ch for e⁺e^? and pp interactions at the same center of mass energy. 〈n_ch〉 and the ratio 〈n_ch/D_ch in e⁺e^? annihilations are significantly larger than in pp collisions and are found to be in overall agreement with QCD predictions. KNO scaling is seen to be satisfied.     

Archaeal C80 isoprenoid tetraacids responsible for naphthenate deposition in crude oil processing

The structure of a novel class of octaterpene tetracarboxylic acids which is responsible for naphthenate deposition in crude oil processing has been determined by NMR and mass spectroscopy.     

Closed form equilibrium evaluation of interest rate caps and related derivatives in a real business cycle setting

The objective of this study is to provide closed form solutions to financial derivatives on mean-reverting cash flows. The general equilibrium real business cycle specification implies that underlying prices follow geometric mean reversion processes. Option-pricing formulas are derived, in terms of macroeconomic parameters or observable market prices, both for consumption goods and interest rates. The framework offers a rich specification of the economy’s yield curve and caplet volatility surface, which seems to fit well with criteria suggested by the empirical literature. The methodology may be useful for studying the effects of real economy changes on financial markets.     

Bayesian estimation of NIG models via Markov chain Monte Carlo methods

The normal inverse Gaussian (NIG) distribution is a promising alternative for modelling financial data since it is a continuous distribution that allows for skewness and fat tails. There is an increasing number of applications of the NIG distribution to financial problems. Due to the complicated nature of its density, estimation procedures are not simple. In this paper we propose Bayesian estimation for the parameters of the NIG distribution via an MCMC scheme based on the Gibbs sampler. Our approach makes use of the data augmentation provided by the mixture representation of the distribution. We also extend the model to allow for modelling heteroscedastic regression situations. Examples with financial and simulated data are provided. Copyright © 2004 John Wiley & Sons, Ltd.