Optical,electrical, and thermochromic properties of polyazothiophene Langmuir–Blodgett films

The conductivity and luminescence of conjugated polymers may be combined with the photoisomerization capability of azobenzene materials to achieve unique properties for a variety of applications, particularly if conjugated polymers with azobenzene side chains are processed as nanostructured films. In this study, we report on Langmuir–Blodgett (LB) films of a polythiophene-bearing azobenzene moieties, which displayed photoluminescence, thermochromism, electroactivity, and photoinduced birefringence. The latter three properties were enhanced in the LB films, as compared to spin-coated films of the polyazothiophene, and this has been attributed to differences in film morphology that could be probed with atomic force microscopy.     

Pump−probe experiments at the TEMPO beamline using the low‐α operation mode of Synchrotron SOLEIL

The SOLEIL synchrotron radiation source is regularly operated in special filling modes dedicated to pump–probe experiments. Among others, the low‐α mode operation is characterized by shorter pulse duration and represents the natural bridge between 50 ps synchrotron pulses and femtosecond experiments. Here, the capabilities in low‐α mode of the experimental set‐ups developed at the TEMPO beamline to perform pump–probe experiments with soft X‐rays based on photoelectron or photon detection are presented. A 282 kHz repetition‐rate femtosecond laser is synchronized with the synchrotron radiation time structure to induce fast electronic and/or magnetic excitations. Detection is performed using a two‐dimensional space resolution plus time resolution detector based on microchannel plates equipped with a delay line. Results of time‐resolved photoelectron spectroscopy, circular dichroism and magnetic scattering experiments are reported, and their respective advantages and limitations in the framework of high‐time‐resolution pump–probe experiments compared and discussed.     

Molecular Complexes of Simple Anions with Electron‐Deficient Arenes: Spectroscopic Evidence for Two Types of Structural Motifs for Anion–Arene Interactions

Anion–π interactions between a π‐acidic aromatic system and an anion are gaining increasing recognition in chemistry and biology. Herein, the binding features of an electron‐deficient aromatic system (1,3,5‐trinitrobenzene (TNB)) and selected anions (OH^?, Br^?, and I^?) are examined in the gas phase by using the combined information derived from collision‐induced dissociation experiments at variable energy, infrared multiple‐photon dissociation spectroscopy, and quantum chemical calculations. We provide spectroscopic evidence for two different structural motifs of anion–arene complexes depending on the nature of the anion. The TNB–OR^? complexes (R=H, or alkyl groups which were studied earlier) adopt an anionic σ‐complex structure whereby RO^? attacks the aromatic ring with covalent bond formation, and develops a tetrahedral ring carbon bound to H and OR. The halide complexes rather conform to a structure in which the TNB moiety is hardly altered, and the halogen is placed on an unsubstituted carbon atom over the periphery of the ring at a C–X distance that is appreciably longer than a typical covalent bond length. The ensuing structural motif, previously characterized in the solid state and named weak σ interaction, is now confirmed by an IR spectroscopic assay in the gas phase, in which the sampled species are unperturbed by crystal packing or solvation effects.     

Investigation of the Aquatic Photolytic and Photocatalytic Degradation of Citalopram

This study investigated the direct and indirect photochemical degradation of citalopram (CIT), a selective serotonin reuptake inhibitor (SSRI), under natural and artificial solar radiation. Experiments were conducted in a variety of different operating conditions including Milli-Q (MQ) water and natural waters (lake water and municipal WWT effluent), as well as in the presence of natural water constituents (organic matter, nitrate and bicarbonate). Results showed that indirect photolysis can be an important degradation process in the aquatic environment since citalopram photo-transformation in the natural waters was accelerated in comparison to MQ water both under natural and simulated solar irradiation. In addition, to investigate the decontamination of water from citalopram, TiO₂-mediated photocatalytic degradation was carried out and the attention was given to mineralization and toxicity evaluation together with the identification of by-products. The photocatalytic process gave rise to the formation of transformation products, and 11 of them were identified by HPLC-HRMS, whereas the complete mineralization was almost achieved after 5 h of irradiation. The assessment of toxicity of the treated solutions was performed by Microtox bioassay (Vibrio fischeri) and in silico tests showing that citalopram photo-transformation involved the formation of harmful compounds.     

In-air broad beam ionoluminescence microscopy as a tool for rocks and stone artworks characterisation

Broad beam ionoluminescence (IL) microscopy is a promising technique for the non-destructive characterisation of rocks and stone objects. Luminescence imaging by means of broad ion beams has been sporadically used by other authors but, to our knowledge, its potential has not yet been fully investigated, neither in geological science nor in other fields. The in-air broad beam IL microscope was developed and installed at the INFN-LABEC external microbeam in Florence. Similar to the cathodoluminescence (CL) microscope, the apparatus exploits a CCD colour camera collecting images (few square millimetres wide, with ~10-μm spatial resolution) of the luminescence emitted by the sample hit by a defocused megaelectron volt (MeV) proton beam. The main differences with the well-established and widespread CL are the possibility of working in air (no sampling or conductive coatings required) and the possibility of combining the analysis with microbeam analysis, such as, for example, μ-IL and μ-PIXE (particle-induced X-ray emission). To show the potential of the technique, IL images of thin sections of lapis lazuli are compared with those obtained by means of an in-vacuum cold CL. An application to the study of stone artworks is also reported. This technique and apparatus will provide a valuable help for interdisciplinary applications, e.g. in geological sciences and in the cultural heritage field.     

On the determination of diameter distribution in multi‐wall carbon nanotubes by Raman spectroscopy: issues related to excitation laser energy

Multi‐wall carbon nanotubes (MWCNTs) produced by the arc discharge between two graphite rods in liquid nitrogen have been investigated with the use of Raman spectroscopy and transmission electron microscopy (TEM). The effects of the applied voltage on the structural properties of the produced MWCNTs have been observed, in particular, as it concerns the size of the innermost and outermost diameters. The apparent discrepancies observed between the Raman and TEM results are explained through the observation of a selective response of the MWCNTs to the excitation laser energy in Raman spectroscopy, similar to the case of single‐wall CNTs. Electronic structure calculations correlate such behavior with optical transitions, in the presence of strong electronic localizations, spatially confined in a few neighboring walls. Copyright © 2011 John Wiley & Sons, Ltd.     

Conformational analysis of quinine and its pseudo enantiomer quinidine: a combined jet-cooled spectroscopy and vibrational circular dichroism study

Laser-desorbed quinine and quinidine have been studied in the gas phase by combining supersonic expansion with laser spectroscopy, namely, laser-induced fluorescence (LIF), resonance-enhanced multiphoton ionization (REMPI), and IR-UV double resonance experiments. Density funtional theory (DFT) calculations have been done in conjunction with the experimental work. The first electronic transition of quinine and quinidine is of π-π* nature, and the studied molecules weakly fluoresce in the gas phase, in contrast to what was observed in solution (Qin, W. W.; et al. J. Phys. Chem. C2009, 113, 11790). The two pseudo enantiomers quinine and quinidine show limited differences in the gas phase; their main conformation is of open type as it is in solution. However, vibrational circular dichroism (VCD) experiments in solution show that additional conformers exist in condensed phase for quinidine, which are not observed for quinine. This difference in behavior between the two pseudo enantiomers is discussed.     

Multilevel optimization for PDAE-constrained optimal control problems with pointwise constraints on control and state

We have developed a fully adaptive optimization environment suitable to solve complex optimal control problems restricted by partial differential algebraic equations (PDAEs) and pointwise constraints on the control [1, 2]. This contribution is devoted to the inclusion of pointwise constraints on the state within the optimization environment. To this end we first give a brief introduction into the architecture of the environment and the inclusion of pointwise constraints on the state by Moreau-Yosida regularization. Then, we test the new tool by applying it to an optimal boundary control problem for the cooling of hot glass down to room temperature, modeled by radiative heat transfer and semi-transparent boundary conditions. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Cysteine-reactive polymers synthesized by atom transfer radical polymerization for conjugation to proteins

In this communication we report a strategy for the synthesis of semitelechelic polymers reactive to cysteines. An initiator modified with a pyridyl disulfide was prepared and used for the CuBr/2,2'-bipyridine-mediated atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate. Polydispersity indices (M(w)/M(n)) of the polymers with different molecular weights were 1.25 or less. The pyridyl disulfide end group was preserved during the polymerization and allowed direct conjugation of the polymer to cysteine residues of bovine serum albumin. The described method provides a general way for the preparation of protein-polymer conjugates through a reversible disulfide bond without the need for postsynthesis modification of the polymers.     

The Effects of Temperature of Condensation on the Thermal Stability and Morphology of 1,4-Phenylenediamine-1-Propylsilica Xerogels

1,4-phenylenediamine-1-propylsilica hybrid xerogels were obtained for two composition at different temperatures of gelation, from 5 up to 70C. The morphological effects produced by the different gelation temperatures were investigated by using N₂ adsorption-desorption isotherms and scanning electron microscopy. The thermal stability of the organic groups and their distribution on the xerogel matrix, i.e. the fraction of the organic groups that were trapped in closed pores, formed during the xerogel synthesis, and the fraction of organic groups present on the surface, were obtained by using infrared thermal analysis. The higher porosity of the xerogels and the higher thermal stability of the organic groups were achieved for samples gelled at 25C.