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Dirk G Kurth

Publications and source records attributed to Dirk G Kurth.

27 records · Page 2Linked to original sources
PubMed2004

Smart polyoxometalate-based nitrogen monoxide sensors.

An electrochemical sensor design for selective NO detection is presented based on a polyoxometalate (POM) cluster immobilized on an electrode through a polyelectrolyte matrix. It is suggested that the POM can electrocatalyze the reduction of NO. The reduction current is proportional to the NO concentration in the investigated concentration window ranging from 1 nM to 10 microM. The sensitivity of the device can be adjusted by the number of immobilized layers. The response to possible interfering reagents such as nitrate and nitrite can be controlled through the multilayer design. By a predominant negatively charged outer surface, the response to these ions is markedly reduced.

Biosensing Techniques↗
PubMed2003

Nanoscopic structure of a metallo-supramolecular polyelectrolyte--amphiphile complex, elucidated by X-ray scattering and molecular modeling.

A combination of molecular modeling and X-ray scattering was used to elucidate the structure of the metallosupramolecular polyelectrolyte--amphiphile complex (PAC) self-assembled from FeII, 1,4-bis(2,2':6,'2"-terpyridin-4'-yl)benzene, and dihexadecyl phosphate (DHP). An approximate structure of the semi-ordered material was derived from the analysis of the X-ray scattering data. The experimental data provided sufficient input for obtaining a useful starting configuration for molecular modeling. Various models of the supramolecular architecture are presented and discussed in terms of their total energies and scattering patterns. In an iterative approach each level of the structural hierarchy was refined until satisfactory agreement of calculated and experimental scattering patterns was reached. The remarkable sensitivity of the simulated scattering curves to even the smallest structural changes at all length scales restricts the arbitrariness of modeling. The final model of PAC consists of flat lamellae of alternating strata of interdigitated DHP monolayers and nematically ordered polyelectrolyte chains.

Journal Article↗
PubMed2002

The structure of self-assembled multilayers with polyoxometalate nanoclusters.

Using electrostatic layer-by-layer self-assembly (ELSA), the formation of multilayers with polyelectrolytes and nanoscopic polyoxometalate (POM) clusters of different sizes and charges is investigated. The multilayers are characterized by UV-vis absorption spectroscopy, optical ellipsometry, cyclic voltammetry, and atomic force microscopy. In all cases, it is possible to find experimental conditions to achieve irreversible adsorption and regular multilayer deposition. Most importantly, the surface coverage is directly related to the total charge of the POM anion and can be controlled from submonolayer to multilayer coverage by adjusting the ionic strength of the dipping solutions. Imaging the interfaces after POM deposition by atomic force microscopy reveals a granular surface texture with nanometer-sized features. The average interfacial roughness amounts to approximately 1 nm. Cyclic voltammetry indicates that the electrochemical properties of the POM clusters are fully maintained in the polyelectrolyte matrix, which opens a route toward practical applications such as sensors or heterogeneous catalysts. Moreover, the permeability toward electrochemically active probe molecules can be tailored through the multilayer architecture and deposition conditions. Finally, we note that despite the low total charge and comparably small size of the discrete POM anions, the multilayers are remarkably stable. This work provides basic guidelines for the assembly of POM-containing ELSA multilayers and provides detailed insight into characteristic surface coverage, permeability, and electrochemical properties.

Journal Article↗
PubMed2002

Structure and properties of the dendron-encapsulated polyoxometalate (C(52)H(60)NO(12))(12)[(Mn(H(2)O))(3)(SbW(9)O(33))(2)], a first generation dendrizyme.

Combining analytical and theoretical methods, we present a detailed study of a heteropolytungstate cluster encapsulated in a shell of dendritically branching surfactants, namely (C(52)H(60)NO(12))(12)[(Mn(H(2)O))(3)(SbW(9)O(33))(2)], 3. This novel surfactant-encapsulated cluster (SEC) self-assembles spontaneously from polyoxometalate-containing solutions treated with a stoichiometric amount of dendrons. Compound 3 exhibits a discrete supramolecular architecture in which a single polyoxometalate anion resides in a compact shell of dendrons. Our approach attempts to combine the catalytic activity of polyoxometalates with the steric properties of tailored dendritic surfactants into size-selective catalytic systems. The structural characterization of the SEC is based on analytical ultracentrifugation (AUC) and small-angle neutron scattering (SANS). The packing arrangement of dendrons at the cluster surface is gleaned from molecular dynamics (MD) simulations, which suggests a highly porous shell structure due to the dynamic formation of internal clefts and cavities. From analysis of the MD trajectory of 3, a theoretical neutron-scattering function is derived that is in good agreement with experimental SANS data. Force field parameters used in MD simulations are partially derived from a quantum mechanical geometry optimization of [(Zn(H(2)O))(3)(SbW(9)O(33))(2)](12)(-), 2b, at the density functional theory (DFT) level. DFT calculations are corroborated by X-ray structure analysis of Na(6)K(6)[(Zn(H(2)O))(3)(SbW(9)O(33))(2)].23H(2)O, which is isostructural with the catalytically active Mn derivative 2a. The combined use of theoretical and analytical methods aims at rapidly prototyping smart catalysts ("dendrizymes"), which are structurally related to naturally occurring metalloproteins.

Journal Article↗
PubMed2002

Polyoxometalates as pH-sensitive probes in self-assembled multilayers.

The polyoxometalate cluster [CoII4(H2O)2P4W30O112]16- (Co-POM) embedded in a self-assembled polyelectrolyte matrix shows a remarkable pH dependence of its electrochemical response, opening a route to use Co-POM as a molecular probe or to fabricate pH microelectrodes.

Journal Article↗
PubMed2002

Metallosupramolecular coordination polyelectrolytes: potential building blocks for molecular-based devices.

Metal-ion-induced self-assembly of ditopic ligands, based on bisterpyridines, and transition metal ions result in formation of metallosupramolecular coordination polyelectrolytes (MEPE). The positive charge of MEPE can be utilized in several ways to process highly ordered architectures. Alternating adsorption of MEPE and oppositely charged polyelectrolytes on solid substrates results in multilayers. The sequential nature of this process allows combining MEPEs with other functional components. This process permits nanometer thickness control, is readily adapted for automated processing, and is applicable to two-dimensional substrates as well as to colloidal templates. The surface chemical properties of MEPE are readily controlled by complexing MEPE with negatively charged amphiphiles. The resulting polyelectrolyte-amphiphile complexes (PAC) are soluble in organic solvents and form liquid crystalline phases. The PAC also spreads at the air-water interface as Langmuir monolayer, which can be transferred onto solid substrates. The resulting Langmuir-Blodgett multilayers are highly ordered and anisotropic. Materials with transition metal ions possess many interesting properties, including spin transitions, magnetism, as well as photochemical assets that are relevant for the construction of functional devices and materials. The presented approach combines principles of supramolecular and colloidal chemistry as well as surface science, is highly modular in nature, and provides extensive control of structure and function from molecular to macroscopic levels.

Air↗