Application of commercially available fluorophores as triplet spin probes in EPR spectroscopy

ABSTRACT

In recent years, photoexcited molecular triplet states became increasingly popular in magnetic resonance, e.g. as spin probes to measure distances relative to other electron-paramagnetic species or as moieties that transfer light-generated electron–spin polarisation of the triplet state to surrounding magnetic nuclei. In this study, the triplet states of three commercially available dyes, Erythrosin B, Rose Bengal and Atto Thio 12, all typically utilised as fluorophores in optical spectroscopies and microscopies, are investigated in aqueous solutions by using transient absorption spectroscopy and transient electron paramagnetic resonance (EPR). From these methods, the triplet-state lifetimes as well as their zero-field splitting parameters, D and E, which reflect the electronic structures of the triplet state wavefunctions, were obtained. Atto Thio 12 exhibits much smaller D and E values as compared to Rose Bengal and Erythrosin B. On the basis of density functional theory calculations of the triplets’ energy splittings at zero magnetic field, these findings were rationalised. As a proof of concept for applications, the triplet-state properties of Atto Thio 12 bound to an aptamer were also determined and the results are discussed.     

The GNG neural network in analyzing consumer behaviour patterns: empirical research on a purchasing behaviour processes realized by the elderly consumers

Advances in Data Analysis and Classification - The paper sheds light on the use of a self-learning GNG neural network for identification and exploration of the purchasing behaviour patterns. The...     

Experimentelle Identifikation viskoelastischer Eigenschaften von Bremsbelägen

Bremsenquietschen ist ein hochfrequentes störendes Geräusch, welches auf reibungsinduzierte selbsterregte Schwingungen des Bremssystems zurückzuführen ist. Dabei verliert die nicht quietschende Konfiguration ihre Stabilität, das Bremssystem beginnt mit wachsenden Amplituden zu schwingen und erreicht schließlich einen Grenzzykel. Bei der mechanisch-mathematischen Modellbildung zur Vorhersage des Bremsenquietschens ist das viskoelastische Verhalten der Reibmaterialien eine der wesentlichen Einflußgrößen. Aufgrund der starken Abhängigkeit der Reibmaterialien von der Art und Höhe der Belastung, wird nachfolgend ein Verfahren zur experimentellen Identifikation ihrer Eigenschaften unter Berücksichtigung von quietschrelevanten Belastungszuständen vorgestellt. Die experimentell identifizierten Parameter werden in ein Mehrkörper-Bremsenmodell einer Kraftfahrzeugscheibenbremse integriert und erste Ergebnisse der nichtlinearen Stabilitätsanalyse vorgestellt. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Screening Papaveraceae as Novel Antibiofilm Natural-Based Agents

The antimicrobial properties of herbs from Papaveraceae have been used in medicine for centuries. Nevertheless, mutual relationships between the individual bioactive substances contained in these plants remain poorly elucidated. In this work, phytochemical composition of extracts from the aerial and underground parts of five Papaveraceae species (Chelidonium majus L., Corydalis cava (L.) Schweigg. and Körte, C. cheilanthifolia Hemsl., C. pumila (Host) Rchb., and Fumaria vaillantii Loisel.) were examined using LC-ESI-MS/MS with a triple quadrupole analyzer. Large differences in the quality and quantity of all analyzed compounds were observed between species of different genera and also within one genus. Two groups of metabolites predominated in the phytochemical profiles. These were isoquinoline alkaloids and, in smaller amounts, non-phenolic carboxylic acids and phenolic compounds. In aerial and underground parts, 22 and 20 compounds were detected, respectively. These included: seven isoquinoline alkaloids: protopine, allocryptopine, coptisine, berberine, chelidonine, sanguinarine, and chelerythrine; five of their derivatives as well as non-alkaloids: malic acid, trans-aconitic acid, quinic acid, salicylic acid, trans-caffeic acid, p-coumaric acid, chlorogenic acid, quercetin, and kaempferol; and vanillin. The aerial parts were much richer in phenolic compounds regardless of the plant species. Characterized extracts were studied for their antimicrobial potential against planktonic and biofilm-producing cells of S. aureus, P. aeruginosa, and C. albicans. The impact of the extracts on cellular metabolic activity and biofilm biomass production was evaluated. Moreover, the antimicrobial activity of the extracts introduced to the polymeric carrier made of bacterial cellulose was assessed. Extracts of C. cheilanthifolia were found to be the most effective against all tested human pathogens. Multiple regression tests indicated a high antimicrobial impact of quercetin in extracts of aerial parts against planktonic cells of S. aureus, P. aeruginosa, and C. albicans, and no direct correlation between the composition of other bioactive substances and the results of antimicrobial activity were found. Conclusively, further investigations are required to identify the relations between recognized and unrecognized compounds within extracts and their biological properties.     

Enhancement of oxygen reduction at Co-porphyrin catalyst by supporting onto hybrid multi-layered film of polypyrrole and polyoxometalate-modified gold nanoparticles

Three-dimensional multi-layered films (on glassy carbon) composed of networks of polyoxometallate (PMo₁₂O₄₀ ³⁻)-modified gold nanoparticles linked together through the alternately deposited ultra-thin layers of polypyrrole have served as active supports for Co-porphyrin catalytic centers. The hybrid organic-inorganic films (supports) have been prepared by using the layer-by-layer approach. The fact that polyanionic (phosphomolybdate) adsorbates on gold nanoparticles are attracted by positively charged sites of conducting polymer (polypyrrole) structures leads to the stabilizing effect and facilitates distribution of Au nanostructures. The systems have been characterized using scanning electron microscopy, as well as with chronoamperometric and voltammetric techniques. By supporting Co-porphyrin centers onto the hybrid film of the polymer-linked phosphomolybdate-stabilized gold nanoparticles, significant electrocatalytic enhancement effects (namely voltammetric current increases) have been observed during the electroreduction of oxygen in acid medium relative to a standard response of the simple porphyrin deposit on glassy carbon measured under analogous conditions. Among important issues is the high activity of the hybrid film (support) itself toward the reductive decomposition of hydrogen peroxide to water. When it comes to performance of the Co-porphyrin-containing system, it is reasonable to expect that the O₂ reduction process is initiated at Co-porphyrin catalytic sites (two-electron reduction to H₂O₂) and continued (two-electron reduction to H₂O) at the hybrid film containing gold nanoparticles dispersed within the highly porous cauliflower-like structures of polypyrrole multi-layers. While the gold networks facilitate charge distribution within the hybrid electrocatalytic film, non-covalent π-π interactions of porphyrin rings with polypyrrole interlayers and charge transfers between negatively charged (PMo₁₂O₄₀ ³⁻ modified) gold nanoparticles and positively charged nitrogen sites of polypyrrole could also cause synergism.

     

Preparation and characterization of carbon foams derived from cyanate esters and cyanate/epoxy copolymers

Journal of Thermal Analysis and Calorimetry - The aim of this study was to obtain carbon foams (CFs) of various pore structure and high mechanical strength using a simple and efficient method to...