DYNMULTIREC

The targets of the project “Dynamic Biomaterials with Multivalent Recognition Properties” (DYNMULTIREC) are focused on: i) the design, fabrication, investigation of properties and applications of highly selective membranes containing directional channels of variable sizes and binding abilities and exhibiting specific and selective permeability for ions (transition metals and lanthanides) and molecules (peptides, modified aminoacids and sugars, aromatic compounds, water), as well as ii) the design and use of the dynamic constitutional polymers (dynamers) functionalized with different biologically relevant moieties (i.e. metallochelating ligands or activity-based probes) for oligomerisation of His-tagged proteins and the synthesis of new protein-decorated polymers. The construction of the membranes (organic-inorganic networks) and of the biodynamers takes into account the following directions: • Adaptive multifunctional membranes based on the incorporation of macrocycles by directed self-assembly into inorganic networks. The challenging idea at this point is the building of the target adaptive multifunctional membranes applying the principles of constitutional dynamic chemistry (CDC). • Multifunctional organic-inorganic membranes having macrocycles within the pores built by the 2D self assembly of sterically compatible aromatic units decorated with complementary multiple H-donor / acceptor groups followed by the 3D self-assembly of these macrocycles and their incorporation into organic-inorganic networks via supramolecular contacts (stacking). The main advantages of this approach consist in the fact that one can obtain a set of appropriately decorated aromatic units which then can be assembled in different macrocycles by simply changing the partners belonging to the same set or, like in the previous case, the shape of the self-assembled macrocycles can be induced and amplified by the molecule which is targeted for separation via host-guest interactions. • Hybrid networks with channels exhibiting highly selective permeability for biomolecules (aminoacids, peptides and modified sugars) based on cyclic peptides made of (LD)n or (LLLD)n sequences. The (LD)n or (LLLD)n sequences ensure in one case a quite planar shape of the macrocycles and on the other case [for the (LLLD)n sequence] that every forth aminoacid has the side chain oriented inside the macrocycle and they can participate in a decisive way to the selectivity of the membrane for different targets. Furthermore, these membranes can be used for enantiomers separation. • The development of new biodynamers as advanced synthetic materials for protein immobilization, protein clustering and multivalent interactions with biological modulators is based on the principle of CDC. To build the Dynamic Constitutional Libraries (DCLs) we turned our sights to the acylhydrazone exchange reaction using a set of di- and tri-aldehydes and acylhyrazones decorated with metallochelating, activity-based probes or proteins. The innovative idea of this project is the design and synthesis of dynamic membranes and dynamers. The membranes are able to modulate the structure of the channels according with the target species which has to be transported through the membrane while the dynamic and adaptive nature of the dynamers will favor the multivalent interactions of the immobilized proteins (protein clustering). The proposed strategy ensures a high selectivity and adaptativity of the membrane using the cooperation of the guest (target) species and offers the possibility to use the same building blocks for the construction of membranes dedicated to the transport of a plethora of species of high variety (ions, sugars, aminoacids, peptides and other biomolecules) and applications (biomedical, environment, resolution of racemics).