Characterization of optical transduction-based molecular systems and nanoparticles for the development of chemical sensors

With the increasing importance that nanotechnologies have in everyday life, it is not difficult to realize that also a single molecule, if properly designed, can be a device able to perform useful functions: such a chemical species is called chemosensor, that is a molecule of abiotic origin that signals the presence of matter or energy. Signal transduction is the mechanism by which an interaction of a sensor with an analyte yields a measurable form of energy. When dealing with the design of a chemosensor, we need to take into account a “communication requirement” between its three component: the receptor unit, responsible for the selective analyte binding, the spacer, which controls the geometry of the system and modulates the electronic interaction between the receptor and the signalling unit, whose physico-chemical properties change upon complexation. A luminescent chemosensor communicates a variation of the physico-chemical properties of the receptor unit with a luminescence output signal. This thesis work consists in the characterization of new molecular and nanoparticle-based system which can be used as sensitive materials for the construction of new optical transduction devices able to provide information about the concentration of analytes in solution. In particular two direction were taken. The first is to continue in the development of new chemosensors, that is the first step for the construction of reliable and efficient devices, and in particular the work will be focused on chemosensors for metal ions for biomedical and environmental applications. The second is to study more efficient and complex organized systems, such as derivatized silica nanoparticles. These system can potentially have higher sensitivity than molecular systems, and present many advantages, like the possibility to be ratiometric, higher Stokes shifts and lower signal-to-noise ratio.

Sustainable processes using heterogeneous acid catalysts. Some examples of industrial interest.

In recent years the need for the design of more sustainable processes and the development of alternative reaction routes to reduce the environmental impact of the chemical industry has gained vital importance. Main objectives especially regard the use of renewable raw materials, the exploitation of alternative energy sources, the design of inherently safe processes and of integrated reaction/separation technologies (e.g. microreactors and membranes), the process intensification, the reduction of waste and the development of new catalytic pathways. The present PhD thesis reports results derived during a three years research period at the School of Chemical Sciences of Alma Mater Studiorum-University of Bologna, Dept. of Industrial Chemistry and Materials (now Dept. of Industrial Chemistry “Toso Montanari”), under the supervision of Prof. Fabrizio Cavani (Catalytic Processes Development Group). Three research projects in the field of heterogeneous acid catalysis focused on potential industrial applications were carried out. The main project, regarding the conversion of lignocellulosic materials to produce monosaccharides (important intermediates for production of biofuels and bioplatform molecules) was financed and carried out in collaboration with the Italian oil company eni S.p.A. (Istituto eni Donegani-Research Center for non-Conventional Energies, Novara, Italy) The second and third academic projects dealt with the development of green chemical processes for fine chemicals manufacturing. In particular, (a) the condensation reaction between acetone and ammonia to give triacetoneamine (TAA), and (b) the Friedel-Crafts acylation of phenol with benzoic acid were investigated.

Assessment and optimization of chemical industrial processes from a life cycle perspective

During the PhD program in chemistry, curriculum in environmental chemistry, at the University of Bologna the sustainability of industry was investigated through the application of the LCA methodology. The efforts were focused on the chemical sector in order to investigate reactions dealing with the Green Chemistry and Green Engineering principles, evaluating their sustainability in comparison with traditional pathways by a life cycle perspective. The environmental benefits associated with a reduction in the synthesis steps and the use of renewable feedstock were assessed through a holistic approach selecting two case studies with high relevance from an industrial point of view: the synthesis of acrylonitrile and the production of acrolein. The current approach wants to represent a standardized application of LCA methodology to the chemical sector, which could be extended to several case studies, and also an improvement of the current databases, since the lack of data to fill the inventories of the chemical productions represent a huge limitation, difficult to overcome and that can affects negatively the results of the studies. Results emerged from the analyses confirms that the sustainability in the chemical sector should be evaluated from a cradle-to-gate approach, considering all the stages and flows involved in each pathways in order to avoid shifting the environmental burdens from a steps to another. Moreover, if possible, LCA should be supported by other tools able to investigate the other two dimensions of sustainability represented by the social and economic issues.