On-line identification of diastereomeric dibenzo[a,l]pyrene diol epoxide-derived deoxyadenosine adducts by capillary electrophoresis-fluorescence line-narrowing and non-line narrowing spectroscopy.

A capillary electrophoretic method for the separation and on-line identification of closely related analytes using low-temperature fluorescence spectroscopy is reported for the eight diastereomeric deoxyadenosine (dA) adducts derived from dibenzo[a,l]pyrene diol epoxide (DB[a,l]PDE). Electrophoretic separation of stereoisomers was accomplished by application of a mixed surfactant buffer [dioctyl sulfosuccinate (DOSS) and Brij-S], which was below the critical micelle concentration (CMC) due to the high concentration (approximately 25%) of organic solvent. Addition of multiple surfactant additives to the separation buffer provided electrophoretic resolution, which was unattainable under single surfactant conditions. It is shown that the CE-separated analyte zones could be identified on-line via low-temperature (4.2 K) fluorescence non-line narrowing and fluorescence line-narrowing (FLN) spectroscopy. In addition, it was determined that in CE buffer trans-syn-,cis-syn- and cis-anti-DB[a,l]PDE-14-N6dA diastereomeric adducts exist mostly with the -dA and DB[a,l]P moiety in an "open"-type conformation while the trans-anti-DB[a,l]PDE-14-N6dA adducts exist in two different conformations whose relative distribution depends on matrix composition. The above conformations have also been revealed by selective laser excitation. Thus, the low-temperature methodology not only provides fingerprint structure via vibrationally resolved 4.2 K fluorescence spectra for adduct identification, but also provides conformational information on the spatial relationship of the carcinogen and dA moiety. These results, taken together with those for DB[a,l]P-DNA adducts formed in standard glasses and mouse epidermis exposed to DB[a,l]P, support our earlier findings that DB[a,l]P-derived adducts exist in different conformations [Jankowiak et al., Chem. Res. Toxicol. 11 (1998) 674]. Therefore, the combination of the separation power of CE and spectral selectivity of low-temperature fluorescence spectroscopy at NLN and FLN conditions provides a powerful methodology which should prove useful for identification of closely related DNA adducts formed at low levels in biological systems.     

Surface chemistry of carbon dioxide

The review discusses how CO₂ surface chemistry has developed since the early 1950s. Emphasis is given to studies of well-characterized surfaces of metals, oxides and some more complex systems involving in particular alkali modified surfaces and also of coadsorbed molecules.     

The synthesis of the africane-type sesquiterpenoid, 1,5,8,8-tetramethyl-tricyclo[8,1,0,02,6]undec-5-en-9-ol-4-one

One of the alcohols derived from rearrangement of humulene-4,5-epoxide has been converted into a keto-alcohol, the angelate ester of which is a naturally-occurring sesquiterpenoid.     

13C and 77Se NMR spectra of thienoisoselenazoles,selenoloisothiazoles, selenoloisoselenazoles and thienoisothiazoles

Measurements are reported of NH exchange rates of urea, thiourea, acetamide and thioacetamide, using line-shape analysis with natural-abundance ¹⁵N NMR spectra. Base-catalyzed NH-proton exchange of thiourea is 30–40 times faster than for urea, while the corresponding acid-catalyzed exchange is 150 times slower. The base-catalyzed proton exchange for thioacetamide is about 1000 times faster than that of acetamide at 25°C, while the corresponding acid-catalyzed exchange is some 260 times slower.     

Noise sources in turbulent gaseous premixed flames

The relationship between mixture flow parameters and the combustion noise from open turbulent premixed gaseous flames is investigated experimentally and it is shown how the overall noise levels and frequency spectra are related to certain flow and geometric parameters and to the turbulence structure of the combustible mixture.     

The breaking of exchange degeneracy in dual unitarisation

The splitting of trajectories with non-vacuum quantum numbers is discussed within the dual unitarisation scheme. The estimated difference in intercepts between vector-tensor trajectories of opposite signatures, such as ? ? A₂ and $\text{K}{}^1\text{?}\text{K}{}^7$, agrees both in sign and magnitude with that deduced from phenomenological analyses.     

E2 nuclear resonance effects in pionic and kaonic atoms

The attenuation due to the E2 nuclear resonance effect has been measured in hadronic atoms using pions with ¹¹¹Cd and ¹¹²Cd, and for kaons with ¹²²Sn. Energies of the relevant X-ray and γ-ray transitions and of the X-ray cascade intensities have also been measured so as to give a self-consistent set of information. The results are found to be in very good agreement with theoretical calculations.     

The3He(γ,2p)n reaction for Eγ=80-170MeV

The cross section for the³He(γ, 2p) reaction has been measured in a complete kinematics experiment in the energy rangeE _γ=80–170 MeV, forθ _P1=θ _P2=90°. This configuration was selected in order to investigate the role of proton-proton final state interactions in the three-body breakup process. The measured proton spectra are seen to be consistent with a prediction using the Watson-Migdal formalism. The magnitude of the observed cross section clearly indicates an enhancement over phase space, presumably due to the strong proton-proton interaction in the final state. The experimental results agree, within their limited statistical accuracy, with a theoretical calculation which includes this effect.     

15N nuclear magnetic resonance spectroscopy. Natural-abundance 15N spectra of aliphatic oximes

¹⁵N chemical shifts of the Z and E isomers of twenty-two ketoximes and fourteen aldoximes have been determined at the natural-abundance level of ¹⁵N, using Fourier transform methods. The influences of π delocalization, methyl substituents and solute concentration on the oxime nitrogen shielding have been determined. The ¹⁵N shifts for oximes of several cycloalkanones have been measured and the influence of ring size on the chemical shifts is discussed.