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Chimica Fisica dei Materiali Avanzati Part 9 – Dendrimers. Laurea specialistica in Scienza e Ingegneria dei Materiali Curriculum Scienza dei Materiali. Nomenclature of dendrimers. Dendrimer synthesis: divergent approach.
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Chimica Fisica dei Materiali AvanzatiPart 9 – Dendrimers Laurea specialistica in Scienza e Ingegneria dei Materiali Curriculum Scienza dei Materiali Corso CFMA. LS-SIMat
Nomenclature of dendrimers Corso CFMA. LS-SIMat
Dendrimer synthesis: divergent approach Pros: highly iterative chemistry – good control on different generations – possibility to go to high generations (i.e. obtain very large dendrimers). Cons: number of reaction steps increases rapidly with generation – poor control on structural defects, particularly on high generations Corso CFMA. LS-SIMat
Dendrimer synthesis: convergent approach Pros: number of reaction steps does not increase rapidly with generations – good control on structural defects – possibility to obtain anisotropic dendrimers Cons: synthesis of large dendrimers is often hindered Corso CFMA. LS-SIMat
Functional dendrimers Functional units at the periphery Functional units in the branching points Functional units in the core Corso CFMA. LS-SIMat
From synthesis to applications • antenna systems • sensors with signal amplification • NLO systems • nano-reactors • drug delivery systems • catalysts • contrast agents in medical diagnosis • molecular batteries • Unimolecular micelles • templates for nanoparticle synthesis • …. Corso CFMA. LS-SIMat
Molecular light-harvesting antennae • An antenna for light harvesting is an organized multicomponent system in which several chromophoric molecular species absorb the incident light and channel the excitation energy to a common acceptor component. • Organization must be achieved in the dimensions of time, energy, and space Corso CFMA. LS-SIMat
Natural antenna systems Structure of the LH2 light-harvesting antenna system of Rhodopseudomonas acidophila which contains rings of 18 (left) and 9 (right) bacteriochlorophyll molecules. The ring of B850 Bchl a molecules The positions of the B800 Bchl a molecules between the helices of the b-apoproteins forming the outer cylindrical wall of the complex. The a-apoproteins are coloured yellow and the b- apoproteins green. Corso CFMA. LS-SIMat
Natural antenna systems - 2 Schematic representation of the overall light harvesting process by LH2 and LH1 antenna complexes in bacterial photosynthesis. RC is the reaction center Kuhlbrandt, Nature, 1995 Corso CFMA. LS-SIMat
Light harvesting sytems Corso CFMA. LS-SIMat
… an example Corso CFMA. LS-SIMat
Dansyl: a commonly used fluorescent dye • highly fluorescent moleculeuseful to probe interactions with: • Protons • metal ions • dyes Absorption and emission spectra in CH3CN:CH2Cl2 5:1 v/v Corso CFMA. LS-SIMat
Chemical sensors Conventional fluorescent sensor Fluorescent sensor with high signal amplification Corso CFMA. LS-SIMat
Sensor of metal ions with signal amplification One Co2+ guest is sufficient to quench each one of the 64 dansyl units, when they are excited J. Am. Chem. Soc. 2000, 122, 10398 Corso CFMA. LS-SIMat
Light controlled drug delivery systems Corso CFMA. LS-SIMat
Medical applications: photodynamic therapy O2 Light absorption 1O2 Singlet oxygen production Corso CFMA. LS-SIMat