Carbon composite electrodes: surface and electrochemical properties

Electrodes based on particulate carbon-epoxy or silicone composites have been formed and characterised using electrochemical methods, scanning electron microscopy and scanning electrochemical microscopy. These composites are rigid, exhibit high electrical conductivity and are stable in organic solvents for prolonged periods. The bulk resistance of the Araldite-M and Araldite-CW2215 based electrodes is low, 130+/-12 and 185+/-15 ohms, respectively. In contrast, the bulk resistance of the silicone based electrodes is 1480+/-112 ohms. The uncompensated resistance of electrochemical cells where the composites act as working electrodes is significantly larger than that expected on the basis of solution resistance alone, i.e., up to 7.5 kohms in the case of the silicone composites. These results are interpreted in terms of the presence of pores within the composite material. The response times of the composite electrodes to changes in the applied potential is between 3.1 and 7.2 ms which, although almost an order of magnitude longer than a comparable glassy carbon electrode, is sufficiently rapid to give useful voltammetric data for scan rates of several V s(-1). Close to ideal reversible cyclic voltammetry is observed for ferrocene under semi-infinite diffusion control for scan rates between 0.01 and 0.1 V s(-1) at the Araldite composites. In contrast, the large resistance associated with the silicone based materials causes quasi-reversible responses to be observed over this range of scan rate. Scan rate dependent cyclic voltammetry and time resolved chronoamperometry responses observed for ferrocene in solution are consistent with those expected for a random array of microelectrodes. Scanning electron microscopy and scanning electrochemical microscopy has been used to image the shape, size and electrochemical activity of the electroactive zones. In the case of Araldite-M, the quality of the electrode surface has been probed by comparing the rate of heterogeneous electron transfer at a composite microelectrode with that found for a carbon fibre electrode. The standard heterogeneous electron transfer rate constant, k degrees , is 6.0+/-0.1 x 10(-3) cm s(-1) for the composite compared to 1.5+/-0.1 x 10(-1) cm s(-1) for the carbon fibre electrode. While the smaller rate constant found for the composite suggests a less pristine surface, k degrees is sufficiently large to support reversible, electron transfer under typical electroanalytical conditions. These fundamental measurements will underpin the development of enzyme based biosensors for use in organic solvents.     

Chromium speciation in liquid matrices: a survey of the literature

A thorough review of the literature published (1983 - March 1999) on chromium speciation in liquid samples is presented, and analytical techniques used in the 404 articles are summarized. The discussion focuses on atomic spectrometric techniques, which are mainly employed for chromium speciation in liquid matrices (134 articles). Details on the type of pretreatment, species, samples, techniques and analytical features of the methodologies proposed are given.     

Chemistry of the phenoxathiins and isosterically related heterocycles. XXV . Synthesis of 1,6-diazathianthrene from 3-mercaptopyridin-2(1H)-thione via a novel dehydrothiolation reaction in the presence of triethylamine

The generation of the dianion of 3-mercaptopyridin-2(1H)-thione with triethylamine in N,N-dimethylform-amide followed by reaction in the presence of 2-chloronitrobenzene fails to give 1-azathianthrene which is formed in good yield when sodium hydride was employed as the base. The principle product isolated from the reaction was instead 1,6-diazathianthrene. Mechanistic considerations are discussed.     

Makroskonische Diffusion von Methanol in einen Natrium-und einen dekationisierten Y-Zeolith

Ohne Zusammenfassung     

Bassianolone: an antimicrobial precursor of cephalosporolides E and F from the entomoparasitic fungus Beauveria bassiana

We have established the chemical structure of (+)-bassianolone (3), the antimicrobial compound precursor of cephalosporolides E and F, and that of the furan metabolite 4 from the entomopathogenic fungus Beauveria bassiana.     

A multicommutated flow system for determination of bismuth in milk shakes by hydride generation atomic fluorescence spectrometry incorporating on-line neutralization of waste effluent

A highly sensitive method was developed for determination of bismuth in milk shakes by multicommutation hydride generation atomic fluorescence spectrometry (HG-AFS) based on off-line sonication for 10 min with aqua regia 8% (v/v) and on-line waste treatment. The instrumentation and chemistry variables were studied in order to provide the best performance. The limit of detection in the original samples, established for a probability level of 99.6% (k = 3), was 1.67 ng/g Bi. The method provides a fast alternative in control analysis with a sampling throughput of 72 h as compared with 31 h obtained by the classical continuous measurement. Additionally, multicommutation reduces waste generation by a factor of 2.6. The consumption of sample, reductant, and blank, as compared with continuous mode HG-AFS, was reduced 9.6, 4.5, and 13.3 times, respectively. To confirm the accuracy of the method, recovery studies were performed, and excellent agreement between multicommutation and continuous measurement-based values was obtained. Application of the developed methodology for bismuth determination in milk shake samples from the Spanish market provided concentrations ranging from 4.2 to 15.0 ng/mL, and good comparability with data obtained by continuous measurements after microwave-assisted total digestion of samples for a 95% probability level and 12 degrees of freedom was found.     

Complexation behavior of a highly preorganized 7,7-diphenylnorbornane-derived macrocycle: towards the design of molecular clocks

The syntheses of two new cyclophane hosts, 4 and 6, are described. The main difference between them is the higher degree of preorganization of 4 as a consequence of the inclusion of the 7,7-diphenylnorbornane (DPN) subunit. The inner cavity of 4 adopts a belt-shaped structure, while 6 has a twisted geometry. In the solid state, the molecules of macrocycle 6 are stacked along an axis to form nanotubular structures. Compounds 4 and 6 form two of the strongest complexes between arene cyclophanes and Ag(+) reported up to date. The silver cation is located inside the cavity of the macrocycles. The stability of 4.Ag(+) is considerably higher than that of 6.Ag(+). The additional stabilization of 4.Ag(+) is attributed to higher preorganization of macrocycle 4. DNMR experiments as well as theoretical calculations carried out with 4.Ag(+) show evidence of Ag(+)-hopping between two different binding sites inside the macrocycle. This phenomenon could be the basis for the design of molecular clocks.     

Entropic barriers in nanoscale adhesion studied by variable temperature chemical force microscopy

Intermolecular interactions drive the vast majority of condensed phase phenomena from molecular recognition to protein folding to particle adhesion. Complex energy barriers encountered in these interactions include contributions from van der Waals forces, hydrogen bonding, and solvent medium. With the spectacular exception of hydrophobic interactions, contributions from the medium are usually considered secondary. We report a variable temperature force microscopy study of the interactions between several hydrogen bonds in different solvents that challenges this point of view. Surprisingly, we observed an increase in the strength of the interaction between carboxylic acid groups in ethanol as the temperature increased. Moreover, when we switched to a nonpolar solvent we observed the opposite behavior: The binding force decreased as the temperature increased. Kinetic model of bond dissociation provided quantitative interpretation of our measurements. We attributed the observed phenomena to a large entropic contribution from the ordered solvent layers that are forming on the probe and sample surfaces upon detachment. The observed reversal in the force vs temperature trend is a manifestation of a transition between thermodynamic and kinetic regimes of unbinding predicted by the model. Our results indicate that entropic barriers dominated by the interactions of solvent molecules with the surface exist in a much wider variety of systems than previously thought.     

Dense subsets of maximally almost periodic groups

A (discrete) group is said to be maximally almost periodic if the points of are distinguished by homomorphisms into compact Hausdorff groups. A Hausdorff topology on a group is totally bounded if whenever there is such that . For purposes of this abstract, a family with a totally bounded topological group is a strongly extraresolvable family if (a)  \vert G\vert$">, (b) each is dense in , and (c) distinct satisfy ; a totally bounded topological group with such a family is a strongly extraresolvable topological group.

We give two theorems, the second generalizing the first.

Theorem 1. Every infinite totally bounded group contains a dense strongly extraresolvable subgroup.

Corollary. In its largest totally bounded group topology, every infinite Abelian group is strongly extraresolvable.

Theorem 2. Let be maximally almost periodic. Then there are a subgroup of and a family such that

(i) is dense in every totally bounded group topology on ;

(ii) the family is a strongly extraresolvable family for every totally bounded group topology on such that ; and

(iii) admits a totally bounded group topology as in (ii).

Remark. In certain cases, for example when is Abelian, one must in Theorem 2 choose . In certain other cases, for example when the largest totally bounded group topology on is compact, the choice is impossible.