Electroactive thiazole derivatives capped with ferrocenyl units showing charge-transfer transition and selective ion-sensing properties: a combined experimental and theoretical study

The synthesis, optical and electrochemical properties, and X-ray characterization of two thiazole derivatives capped by ferrocenyl groups (5 and 7) and their model compounds with one ferrocenyl, either at 2 or 5 position of the mono- or bis-thiazolyl rings (3, 9, 11, and 14), are presented. Bisferrocenyl thiazole 5 forms the mixed-valence species 5*+ by partial oxidation which, interestingly, shows an intramolecular electron-transfer phenomenon. Moreover, the reported heteroaromatic compounds show selective ion-sensing properties. Thus, ferrocenylthiazoles linked across the 5 position of the heteroaromatic ring are selective chemosensors for Hg2+ and Pb2+ metal ions; 5-ferrocenylthiazole 3 operates through two channels, optical and redox, for Hg2+ and only optical for Pb2+, whereas 1,1'-bis(thiazolyl)ferrocene 14 is only an optical sensor for both metal ions. Moreover, complex 3 behaves as an electrochemically induced switchable chemosensor because of the low metal-ion affinity of the oxidized 3*+ species. On the other hand, ferrocenylthiazole 9, in which the heterocyclic ring and the ferrocene group are linked across the 2 position, is a selective redox sensor for Hg2+ metal ions, and it responds optically, as does bis(thiazolyl)ferrocene 11, to a narrow range of cations (Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+). Finally, bis(ferrocenyl)thiazole 5 is a dual optical and redox sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+, whereas bis(ferrocenyl) compound 7, bearing a bis(thiazole) unit as a bridge, is only a chromogenic sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+. The experimental data and conclusions about both the electronic and ion-sensing properties are supported by DFT calculations which show, in addition, an unprecedented intramolecular electron-transfer reorganization after the first one-electron oxidation of compound 5.     

Multilinear Operator Ideals Associated to Saphar Type (<Emphasis Type="Italic">n</Emphasis> + 1)-tensor Norms

We study an (n + 1)-tensor norm generalizing Saphar’s classic norm to (n+1)-fold tensor products.We characterize the maps in the minimal and maximal multilinear operator ideals related to in the sense of Defant and Floret. Partially supported by the MEC and FEDER project MTM2004-02262 and AVCIT group 03/050.     

Real‐time measurement of H/D exchange in a microdialysis Raman quartz cell

We present here a novel quartz cell for monitoring H/D exchange in biomolecules using Raman spectroscopy. This cell is combined with a syringe to pump heavy water through a hollow microdialysis fibre, which is inserted into the cell. The deuterium efflux into the sample has been studied as a function of the molecular weight cut‐off of the microdialysis fibre and compared with other microcell systems comprising conventional glass capillaries. The fastest D₂O efflux that we have obtained (k_d = 0.38 ± 0.008 min⁻¹) permits to measure exchange rates of 2.5 min⁻¹ or less. Application of this cell to deuterium exchange in glyceraldehyde‐3‐phosphate dehydrogenase reveals a class of H‐atoms highly resistant to deuteration, which is consistent with a previous infrared study on this protein. Copyright © 2009 John Wiley & Sons, Ltd.     

Optical spectroscopy of neodymium-doped calcium barium niobate ferroelectric crystals

In this work, the optical absorption, luminescence and Raman spectra of a single Ca_0.28Ba_0.72Nb₂O₆:Nd³⁺ ferroelectric crystal have been measured and compared to those obtained for the self-frequency solid-state laser converter Sr_0.61Ba_0.39Nb₂O₆:Nd³⁺ crystal. The calcium-niobate system displays a much higher transition temperature (∼150 °C) than the strontium-niobate one (∼80 °C) and so it appears as an excellent candidate for a self-frequency converter solid-state laser, more stable to pumping radiation that than based on the strontium-niobate one.     

Metal–Organic Spheres as Functional Systems for Guest Encapsulation

Music of the spheres : Infinite coordination polymerization of Zn²⁺ ions and a multitopic ligand produces metal–organic micro‐ and nanospheres that can be used as functional matrices. The spheres can encapsulate combinations of active substances, such as organic dyes, magnetic nanoparticles, or luminescent quantum dots (see image), which results in spheres that are luminescent in the blue, green, and red regions of the spectrum.

     

Improving real-time measurement of H/D exchange using a FTIR biospectroscopic probe

We describe the improvement of a novel approach to investigating hydrogen/deuterium (H/D) exchange kinetics in biomolecules using transmission infrared spectroscopy. The method makes use of a Fourier transform infrared spectrometer coupled with a microdialysis flow cell to determine exchange rates of labile hydrogens. With this cell system, the monitoring of exchange reactions has been studied here as a function of some cell characteristics such as: (a) dialysis membrane surface contacting both the H₂O and D₂O compartments; (b) molecular cutoff of dialysis membrane; and (c) distance between the cell-filling holes. The best improvement has been obtained by increasing the dialysis membrane surface followed by increase of molecular cutoff. However, not significant differences were found using various distances between filling holes. The fastest exchange rate which can be measured with the cell system used here is found to be k = 0.41 ± 0.02 min⁻¹, that is, about threefold greater than the one got in a previous work. This microdialysis flow cell has been used here for the study of H/D exchange in nucleic acids with subsequent structural analysis by 2D correlation spectroscopy.     

Bootstrap for estimating the MSE of the Spatial EBLUP

This work assumes that the small area quantities of interest follow a Fay–Herriot model with spatially correlated random area effects. Under this model, parametric and nonparametric bootstrap procedures are proposed for estimating the mean squared error of the empirical best linear unbiased predictor (EBLUP). A simulation study based on the Italian Agriculture Census 2000 compares bootstrap and analytical estimates of the MSE and studies their robustness to non-normality. Results indicate lower bias for the non-parametric bootstrap under specific departures from normality.      

Discrete solitons and nonlinear surface modes in semi-infinite waveguide arrays

We discuss the formation of self-trapped localized states near the edge of a semi-infinite array of nonlinear optical waveguides. We study a crossover from nonlinear surface states to discrete solitons by analyzing the families of odd and even modes centered at finite distances from the surface and reveal the physical mechanism of the nonlinearity-induced stabilization of surface modes.