Determination of calcium ion in oil-based drilling fluids with an ion-selective electrode

Calcium ion is determined in the internal phase of oil-based drilling fluids with a calcium ion-selective electrode after treatment with a 1:1 (v/v) xylene/isopropanol mixture and 4 M potassium chloride. Results obtained by this potentiometric method and by the Magcobar titration on laboratory-prepared muds and on a North Sea field mud (Statfjord) were in satisfactory agreement.     

Multiple polypeptide forms observed in two-dimensional gels of Methylococcus capsulatus (Bath) polypeptides are generated during the separation procedure

We have examined two-dimensional electrophoresis (2-DE) gel maps of polypeptides from the Gram-negative bacterium Methylococcus capsulatus (Bath) and found the same widespread trains of spots as often reported in 2-DE gels of polypeptides of other Gram-negative bacteria. Some of the trains of polypeptides, both from the outer membrane and soluble protein fraction, were shown to be generated during the separation procedure of 2-DE, and not by covalent post-translational modifications. The trains were found to be regenerated when rerunning individual polypeptide spots. The polypeptides analysed giving this type of trains were all found to be classified as stable polypeptides according to the instability index of Guruprasad et al. (Protein Eng. 1990, 4, 155-161). The phenomenon most likely reflects conformational equilibria of polypeptides arising from the experimental conditions used, and is a clear drawback of the standard 2-DE procedure, making the gel picture unnecessarily complex to analyse.     

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.     

Nucleophilic reactions of charge delocalised carotenoid mono- and dications

In the present study insight was gained on the larger complexity of cationic mixtures of diaryl (phi,phi-carotene, isorenieratene) and aliphatic (psi,psi-carotene, lycopene) carotenes, prepared by reaction with BF3-etherate, compared with beta,beta-carotene. Chemical reactions of the mono- and dications prepared in situ from the allylic carotenols beta,beta-caroten-4-ol (isocryptoxanthin) and beta,beta-carotene-4,4'-diol (isozeaxanthin), and from isorenieratene and lycopene were investigated using selected O, N and S nucleophiles; water, methanol, azide and thioacetate. In total 22, including 18 new, neutral carotenoid products were isolated and identified by VIS, MS and NMR (in part) spectroscopy. Their structures were compatible with the structures of the cationic intermediates. The formal addition of hydride to the various dications, required to rationalise minor reaction products, is discussed in terms of more likely hydrogen radical or proton transfer in cationic reactions. Extensive E/Z isomerisation was observed for all quenching products. The potential use of carotenoid cations for the synthesis of 4,(4')-substituted beta,beta-carotenes and 7-oxabicyclo[2,2,1]heptane derivatives is discussed.     

Synthesis of 8-Halopurines by Reaction of Lithiated Purines with Appropriate Halogen Donors

Purines lithiated in the 8-position, can be trapped with hexachloroethane, dibromotetrachloroethane, cyanogen bromide and cyanogen iodide, to give a variety of 8-halopurines in excellent yields.     

Dielectric properties of thin-film ZrO<Subscript>2</Subscript> up to 50 GHz for RF MEMS switches

The dielectric properties of zirconium dioxide (ZrO₂) ceramic thin films were characterized up to 50 GHz using coplanar waveguides (CPWs) and metal–insulator–metal (MIM) capacitors with top circular electrodes. The ZrO₂ films were deposited using a chemical solution onto high-resistivity Si wafers and metal layers. The real part of the dielectric constant of approximately 22 and 26 was extracted at 50 GHz for CPW and MIM structures, respectively, and the loss tangent was approximately 0.09 at 50 GHz. C–V and I–V measurements were carried out to determine low-frequency and DC dielectric properties. The measurement results indicate that ZrO₂ is a promising material to be used as a dielectric layer for radio-frequency (RF) microelectromechanical systems (MEMS) capacitive switches.     

Joint seismic-infrasonic processing of recordings from a repeating source of atmospheric explosions

A database has been established of seismic and infrasonic recordings from more than 100 well-constrained surface explosions, conducted by the Finnish military to destroy old ammunition. The recorded seismic signals are essentially identical and indicate that the variation in source location and magnitude is negligible. In contrast, the infrasonic arrivals on both seismic and infrasound sensors exhibit significant variation both with regard to the number of detected phases, phase travel times, and phase amplitudes, which would be attributable to atmospheric factors. This data set provides an excellent database for studies in sound propagation, infrasound array detection, and direction estimation.     

Line-by-line calculations of thermal infrared radiation representative for global condition: CFC-12 as an example

We estimate a current direct radiative forcing due to CFC-12 of 0.18 Wm^-2, which is likely to be the peak radiative forcing for CFC-12. Global measurements of CFC-12 show at present an almost negligible trend for CFC-12 and measurement in an industrialized region show evidence that the peak concentration is reached. It is expected that concentration of CFC-12 in industrialized regions begins to decline 1-3 years before the global concentration.Our radiative forcing calculations are based on a line-by-line model appropriate for simulation of global mean radiative forcing, including clouds and stratospheric temperature adjustment. The radiative forcing of 0.33 Wm^-2/ppbv is close to earlier published results for this compound. New spectroscopic measurements for CFC-12 are performed and compared to previously published results.     

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.     

Angular variation of linewidths in single-crystal EPR spectra

We present the angular variation of the resonance magnetic fields as well as the angular variation of the linewidths obtained from single-crystal electron paramagnetic resonance spectra of Delta+ [Cr((-)chxn)(3lambda lambda lambda)]3+ (chxn = trans-1,2-cyclohexanediamine) doped into the nitrate salt of the isostructural Rh(III) ion Delta+ [Rh((-)chxn)(3lambda lambda lambda](NO3)3)3.H2O. An analysis of the angular variation of the resonance magnetic fields indicates axial symmetry for the cation. An analysis of the angular variation of the linewidths, on the other hand, reveals that not all the paramagnetic sites have perfect axial symmetry.