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.     

Fabrication of anisotropic porous silica monoliths by means of magnetically controlled phase separation in sol-gel processes

Sol-gel accompanied by phase separation is an established method for the preparation of porous silica monoliths with well-defined macroporosity, which find numerous applications. In this work, we demonstrate how the addition of (superpara)magnetic nanocolloids as templates to a system undergoing a sol-gel transition with phase separation leads to the creation of monoliths with a strongly anisotropic structure. It is known that magnetic nanocolloids respond to the application of an external magnetic field by self-assembling into columnar structures. The application of a magnetic field during the chemically driven spinodal decomposition induced by the sol-gel transition allows one to break the symmetry of the system and promote the growth of elongated needle-like silica domains incorporating the magnetic nanocolloids, aligned in the direction of the field. It is found that this microstructure imparts a strong mechanical anisotropy to the materials, with a ratio between the Young's modulus values measured in a direction parallel and perpendicular to the one of the field as high as 150, and an overall smaller average macropores size as compared to isotropic monoliths. The microstructure and properties of the porous monoliths can be controlled by changing both the system composition and the strength of the applied magnetic field. Our monoliths represent the first example of materials prepared by magnetically controlling a phase transition occurring via spinodal decomposition.     

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)     

Intermediate width structures in the 12C(12C,8Beg.s.)16O reaction at E c.m. =20 to 30 MeV

The ¹²C(¹²C,⁸Be_g.s.)¹⁶O reaction cross section has been measured at center-of-mass energies between 20 and 30 MeV. Intermediate width structures have been observed for the reactions leading to the ground state and two doublets of states, 6.05/6.13 MeV and 6.92/7.12 MeV, in ¹⁶O. For the ⁸Be_g.s.+¹⁶O_g.s. channel the dominant angular momenta contributing to several structures have been deduced by the analysis of the excitation functions at selected center-of-mass angles. Correlations between the structures in the ⁸Be_g.s.+¹⁶O_g.s. channel and in other inelastic scattering channels in the E _c.m. = 30 MeV region are discussed. An interpretation of the resonances in terms of current structural models is given     

Three-α-particle reactions in kinematical star conditions

The¹⁰B(d, )⁴He reaction was studied at energies between 4.2 and 6.6 MeV in kinematical plane-star conditions with special emphasis on sequential processes through the⁸Be state of 11.4 MeV. The results are compared with predictions of the Quebert model.Dedicated to Profs. Erich Schmid and Ivo laus on the occasion of their 60th birthdays     

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.     

Aggregation kinetics of polymer colloids in reaction limited regime: experiments and simulations

The kinetics of reaction-limited cluster aggregation of fluorinated polymer colloids in a broad range of particle volume fractions has been investigated experimentally by measuring independently the Fuchs stability ratio W and the time evolution of both the average radius of gyration and the average hydrodynamic radius of the aggregates mass distribution. The W value is determined from the aggregation rate at the very initial stage of the aggregation, where the presence of triplets is negligible. The time evolutions of and are then simulated using the cluster mass distribution calculated from the population balance equations with various aggregation kernels proposed in the literature. It is found that, when the measured W value is used, the only kernels that can correctly simulate the experimental results are the product kernel and the one derived by Odriozola et al. (Europhys. Lett. 53 (2001) 797), with some proper tuning of the exponent in the kernel. For the particle volume fraction phi<1%, the obtained value for the exponent is 0.4 and independent of phi, while it tends to decrease for larger phi values, most likely indicating a significant effect of multi-body interactions on the aggregation kinetics.     

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.