Electronic coupling and scaling effects during dielectric barrier electrospray ionization

The mechanism of the previously published technique of dielectric barrier electrospray ionization (DB-ESI) was investigated in more detail. Two independent current signals occurring during the DB-ESI could be explained and allocated to sub-processes. The modulated shape of the HV signal, the applied frequency as well as the inner diameter of the emitter capillary have a big impact on the spray. Furthermore, there exists a cut-off frequency which depends on the electronic properties of the DB-ESI interface. Comparable mass spectra for lysine employing both conventional ESI and DB-ESI show a good analytical potential of the new technique.     

Diophantine equations and the generalized Riemann hypothesis

We show that, for a listable set P of polynomials with integer coefficients, the statement “for all roots θ of all polynomials in P, the generalized Riemann hypothesis for Q(θ) holds” is Diophantine. That is, the statement is equivalent to the unsolvability of a particular Diophantine equation. This is achieved by finding a decidable property P such that the aforementioned statement may be written in the form “P holds for all natural numbers”.     

The Edge Correlation of Random Forests

The conjecture was made by Kahn that a spanning forest F chosen uniformly at random from all forests of any finite graph G has the edge-negative association property. If true, the conjecture would mean that given any two edges ε₁ and ε₂ in G, the inequality \mathbbP(e₁ ? F, e₂ ? F) ￡ \mathbbP(e₁ ? F)\mathbbP(e₂ ? F){{\mathbb{P}(\varepsilon_{1} \in \mathbf{F}, \varepsilon_{2} \in \mathbf{F}) \leq \mathbb{P}(\varepsilon_{1} \in \mathbf{F})\mathbb{P}(\varepsilon_{2} \in \mathbf{F})}} would hold. We use enumerative methods to show that this conjecture is true for n large enough when G is a complete graph on n vertices. We derive explicit related results for random trees.     

Electron-transfer reactions at the plasma-liquid interface

Electrochemical reactions are normally initiated in solution by metal electrodes such as Pt, which are expensive and limited in supply. In this Communication, we demonstrate that an atmospheric-pressure microplasma can act as a gaseous, metal-free electrode to mediate electron-transfer reactions in aqueous solutions. Ferricyanide is reduced to ferrocyanide by plasma electrons, and the reduction rate is found to depend on discharge current. The ability to initiate and control electrochemical reactions at the plasma-liquid interface opens a new direction for electrochemistry based on interactions between gas-phase electrons and ionic solutions.     

Fullerenes without symmetry: crystallographic characterization of C1(30)-C90 and C1(32)-C90

Fullerenes are generally considered as highly symmetric, yet fullerene isomers with only C(1) symmetry, such as C(1)(30)-C(90) and C(1)(32)-C(90) whose structures are reported here, become increasingly numerous as fullerene size increases.     

Imidazole-modified porphyrin as a pH-responsive sensitizer for cancer photodynamic therapy

5,10,15,20-Tetrakis(N-(2-(1H-imidazol-4-yl)ethyl)benzamide)porphyrin produced twice as many singlet oxygen ((1)O(2)) molecules at pH 5.0 (quantum yield 0.53 ± 0.01) than at pH 7.4, whereas the (1)O(2) quenching rate was reduced by a factor of 2.5 for a pH change from 7.4 to 5.0.     

Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base

Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.     

Analysis of stop consonant production errors in developmentally dysphasic children

The speech production skills of 12 dysphasic children and of 12 normal children were compared. The dysphasic children were found to have significantly greater difficulty than the normal children in producing stop consonants. In addition, it was found that seven of the dysphasic children, who had difficulty in perceiving initial stop consonants, had greater difficulty in producing stop consonants than the remaining five dysphasic children who showed no such perceptual difficulty. A detailed phonetic analysis indicated that the dysphasic children seldom omitted stops or substituted nonstop for stop consonants. Instead, their errors were predominantly of voicing or place of articulation. Acoustic analyses suggested that the voicing errors were related to lack of precise control over the timing of speech events, specifically, voice onset time for initial stops and vowel duration preceding final stops. The number of voicing errors on final stops, however, was greater than expected on the basis of lack of differentiation of vowel duration alone. They appeared also to be related to a tendency in the dysphasic children to produce final stops with exaggerated aspiration. The possible relationship of poor timing control in speech production in these children and auditory temporal processing deficits in speech perception is discussed.     

Epoxidation of olefins by hydrogen peroxide in the presence of tetrachloroacetone

1,1,3,3-Tetrachloroacetone, an inexpensive, commercially available material, has been shown to be effective in mediating the hydrogen peroxide oxidation of a variety of olefins to epoxides. The chloroacetone is readily recovered for re-use.