Control of dark current in photoelectrochemical (TiO2/I--I3-)) and dye-sensitized solar cells

The ruthenium complex bis-tetrabutylammonium cis-dithiocyanato-N,N'-bis-2,2'-bipyridine-4-carboxylic acid, 4'-carboxylate ruthenium(II), N-719, was found to block the dark current of dye sensitized solar cells (DSC), based on mesoporous TiO2 films deposited on a F-doped tin oxide electrode and the effect was compared to surface treatment by TiCl4 and the introduction of a compact TiO2 blocking layer.     

Electrochemical metallization of self-assembled porphyrin monolayers

Multifunctional sensor systems are becoming increasingly important in electroanalytical chemistry. Together with ongoing miniaturization there is a need for micro- and nanopatterning tools for thin electroactive layers (e.g. self-assembling monolayers). This paper documents a method for production of a micro-array of different metal-porphyrin monolayers with different sensor properties. A new method has been developed for the selective and local metallization of bare porphyrin monolayers by cathodic pulsing and sweeping. The metal-porphyrin monolayers obtained were characterized by cyclic voltammetry. It was shown that porphyrin monolayers can be metallized with manganese, iron, cobalt, and nickel by use of the new method. It is expected that all types of metal-porphyrin monolayers can be produced in the same manner.     

Analytical separation techniques for the determination of chemical warfare agents

Today, the determination of chemical warfare agents (CWAs) is an important area of application in analytical chemistry. Chromatographic, capillary electrophoretic and mass spectrometric techniques are primarily used for the identification and quantification of a broad field of classical CWAs in environmental samples and neutralization masses, obtained after destruction of CWAs. This overview is illustrative for the state of the art and mainly focuses on the literature published since 1996.     

Microcolumn liquid chromatography of the enantiomers of organophosphorus pesticides with thermionic and ultraviolet detection

Microcolumn liquid chromatography (micro-LC) of some chiral organophosphorus pesticides has been studied using Chiralcel OD columns and simultaneous ultraviolet (UV) and phosphorus selective detection, the latter by means of a micro-UV cell coupled on-line to a thermionic detector (TID). Micro-LC showed a ca. 5-fold improved separation impedance, a ca. 1.8-fold increased column permeability, and greater inertness compared with conventional LC. By using the TID, organophosphorus pesticides could be satisfactorily determined at trace levels, the detection limit being 4 pg/s of phosphorus. The response of the micro-LC-TID system is linear in the range of 0.05–20 ng (r = 0.9994).     

On the rank of truncated incidence matrices of linear spaces

It is well known that for every finite linear space the number b of lines is greater or equal to the number v of points of the space. In this paper we investigate the relation between the nonnegative integer b - v and suitable configurations of subspaces of a linear space.     

Biosynthesis of cervimycin C, an aromatic polyketide antibiotic bearing an unusual dimethylmalonyl moiety

Cervimycin C is the major component of an antibiotic complex produced by Streptomyces tendae HKI-179 consisting of a tetracycline-type aglycon, six tridesoxysugars and a rare dimethylmalonyl moiety. The biosynthetic origin of cervimycin was studied by molecular studies and feeding experiments, which reveal that the dimethylmalonate unit is not derived from malonate, but from valine.     

Pulling tethers from adhered vesicles

The competition between adhesion and tether formation in bound vesicles is investigated. A theoretical model is developed in which tethers are induced by the application of a pulling force to the top of a strongly adhered vesicle. A critical onset force is identified where the tether spontaneously appears as part of a first order shape transition. Further growth of the tether initiates a detachment process that culminates in a continuous unbinding of the vesicle at a finite detachment force. Both critical forces, as well as all shape parameters, are calculated as a function of the reduced volume and the strength of adhesive potential.     

Photodissociation of HCl and small (HCl)m complexes in and on large Ar n clusters

Photodissociation experiments were carried out at 193 nm for single HCl molecules which are adsorbed on the surface of large Ar n clusters and small (HCl)m complexes which are embedded in the interior of these clusters. For the surface case the size dependence is measured for the average sizes n=140-1000. No cage exit events are observed in agreement with the substitutional position of the molecule deeply buried in the outermost shell. This result is confirmed by a molecular dynamics simulation of the pickup process under realistic conditions concerning the experiment and the interaction potentials. The calculations of the dissociation process employ the surface hopping model. For the embedded case the average sizes covered are m=3 and 6 and n=8-248. The kinetic energy of the H atom fragments is measured exhibiting peaks at zero and around 2.0 eV which mark completely caged and unperturbed fragments, respectively. The ratio of theses peaks strongly depends on the cluster size and agrees well with theoretical predictions for one and two closed icosahedral shells, in which the nonadiabatic coupling of all states was accounted for.