Radiation induced competitive chlorination

The -radiolysis of solutions of benzene and naphthalene in carbon tetrachloride has been studied to obtain information about chlorination reactions. The position of naphthalene showed a reactivity 2.5 higher with respect to benzene, while the absence of 2-chloronaphthalene among the products confirmed the relatively high activation energy required for the attack in position.     

Intramolecular electronic interactions in conjugated ferrocene-pi-extended-tetrathiafulvalene donor-pi-donor molecular hybrids

The synthesis of new hybrid ferrocene and pi-extended tetrathiafulvalene (TTF) donor(1)-pi-donor(2) molecular assemblies 16a-c has been carried out by a Wittig-Horner reaction of the respective phosphonate esters 15a-c with 2-(2-ferrocenylvinyl)-9, 10-anthraquinone (18) prepared by olefination of ferrocenecarboxaldehyde (14) and the anthraquinone phosphonium salt 17. Electrochemical studies show that the D(1)-pi-D(2) (D = donor) molecular assemblies 16a-c essentially retain the redox characteristics of both ferrocene and the pi-extended TTF components and the effects of solvent, temperature, scan rate, and working electrode are significant. Most importantly, pronounced intramolecular electronic interactions between the two donor moieties were observed by cyclic voltammetry and Osteryoung square wave voltammetry in both the ground and charged states. Semiempirical calculations support the electrochemical observations.     

Studies on the mechanism of action of azinomycin B: definition of regioselectivity and sequence selectivity of DNA cross-link formation and clarification of the role of the naphthoate

Evaluation of the sequence selectivity, noncovalent association, and orientation of the DNA cross-linking agent azinomycin B on its duplex DNA receptor is described. A strong correlation between sequence nucleophilicity and cross-linking yield was observed, and steric effects due to the thymine C5-methyl group were identified. Detailed studies on the role of the azinomycin naphthoate using viscometry, fluorescence contact energy transfer, and DNA unwinding assays point to a nonintercalative binding mode for this group. A kinetic assay for agent regioselectivity was used to determine the orientation of binding and covalent cross-link formation.     

Phenyl radicals react with dinucleoside phosphates by addition to purine bases and H-atom abstraction from a sugar moiety

Laser-induced acoustic desorption combined with mass spectrometry has been used to demonstrate that phenyl radicals can attack dinucleoside phosphates at both the sugar and base moieties, that purine bases are more susceptible to the attack than pyrimidine bases, and that the more electrophilic the radical, the more efficient the damage to dinucleoside phosphates.     

Very-large-volume sampling of water in gas chromatography using the through oven transfer adsorption desorption (TOTAD) interface for pesticide-residue analysis

The Through Oven Transfer Adsorption Desorption (TOTAD) interface is used to directly introduce large volumes of water (1 mL or more) into a capillary gas chromatograph. The TOTAD interface is a greatly modified programmed temperature vaporizer injector incorporating changes that affect the pneumatics, sample introduction, solvent elimination, and operation mode. The system can easily be automated. The technique is applied to the analysis of pesticide residue in standard solutions and real water samples from the Ebro River (northeastern Spain). The speed of sample introduction was 1 mL/min, and the solvent elimination was almost complete. A nitrogen phosphorous detector is used, and the relative standard deviation varied from 5.7% to 11.7% for the absolute peak areas. The sensitivity achieved by introducing 1 mL of the sample is sufficient for most pesticide-residue analyses in water. The limits of detection ranged from 0.5 to 8.1 ng/L.     

The mean spherical model in a random external field and the replica method

We provide a quick elementary solution of the mean spherical model in a random external field. This also allows an immediate proof of the self-averaging property of the free energy. We calculate the free energy by means of the replica method, i.e., for any (not necessarily integer) replica numbern, and show that when a phase transition occurs the limits andn 0 are not interchangeable.