Biomimetic Polyaminoacids as Precursors for Optical-Active

نویسنده

  • G. Popova
چکیده

Three main types of light-sensitive polyaminoacids (PAA) such as: rod-like dyes contained; photoactive rotaxanes; inorganic-organic cyclophosphazene hybrids are considered in context of intelligent materials creations. Lightmanipulative biomimetics preparation involves strategy via combinatorial synthesis; computation and modelling of possible molecular architecture; self-organization and supramolecular phase formation; function on nanoscale; stimularesponsive study; intelligent materials formation. Modified polyglutamic acid with dyes regular set possesses specific ability to self-assembly with cooperative rearrangement under outer temperature (carbocyanines bonded), pH (fluoresceine bonded). Ion-sensitivity of photoactive peptide (oligo-glutamic or oligo-glycine) rotaxanes is promissive feature for molecular switches construction. Inorganicorganic hybrids with cyclophosphazene cores (star-like design of poly-glutamic or poly-alanine) are the convient matrixes for different fragments immobilization that can result to light-controlled conformations of PAA in variable states: solution, gel, film. Introduction During last decade, a lot of investigators paid attention to Stimula-responsive-“intelligent”material creation that could work in nanoscale. The formation and function of these substances in Supramolecular phase is key fundamental problem nowadays [1]. Different building blocks, which are sensitive to outer factors as temperature, pH, illumination, electric and magnetic fields, etc, can be used for material construction. These materials may exist in various forms, such as solutions, gels, liquid crystals, layers, films [1, 2, 3]. Biomimetic “intelligent materials” have a good perspective for imitation of the natural objects. From this point of view, the modified artificial polypeptides cause current research interest. They can form the β-sheet or α-helical conformations as it is in real proteins. The particular case is polyaminoacids consisting of only one type of aminoacid. They can produce the helical rigid-rod macromolecules deserving a special study. Particularly, introduction of different chromophores dyes, photochromes, luminophores results to new properties, closed to natural. The well-defined rod-like and hairy-rod structures of polyglutamic acid derivatives (PGAD), their abilities to conformational changes, reversible Arrangements permit to investigate variable properties useful for biomedicine, molecular electronics, optical and sensor devices [3, 4, 5]. Intensive research weredevoted to peptide based rotaxanes [6, 7]. The presence of multicentres for hydrogen, ionic and other bindings is favorable for controlled moving construction. Rotaxanes can be used as sensitive elements for “molecular machines” [8] as models of light-, electroor ion-driving shuttle or switches. Previously, cyclopeptides containing one or two crown-ethers produce Supramolecular complexes with functional Spiropyranes. Quantum Chemistry methods were applied for Simulation, Modelling and Optimization of possible Molecular Architectures of photoactive complexes. The size of cyclopeptide cavity defines intraor intermolecular complexation. Several co-polymers were synthesized and tested as sticks in depend upon ring moving. Reversible process irradiation / metalloion containing results to switches available to intelligent systems creation. Mimic protein tertiary structure is founded on the template-assembled concept and is one of the convenient methods that have been used for this aim. Linear or cyclic peptide templates have been used for covalently binding of parallel α-helical peptides [9, 10, 11, 12]. Cyclic peptides, tris-bypyridyn metal complex, porphirine were applied as templates for formation of folded tertiary peptide structures [9, 10, 11]. Tetraphenylporphyrin as a more rigid template for a four-helix proton channel building [12]. The nine-residue peptide template has been utilized for chemoselective ligation [12] of unprotected peptide segments resulting in the total chemical synthesis of protein analogs of native topology. An amido amine dendrimer cyclotriphosphazene [13] have been successfully applied for assembling oligopeptide chains by graft polymerization on surface. It was found that the organized oligopeptide onto a dendrimer template results in drastic enhancement in helicity of the peptide segment. All these points became reasonable basis for our investigations on peptide Intelligent Systems construction. Presently we discuss several properties of biomimetic polyaminoacid derivatives in solutions, monolayers and LangmuirBlodgette films. Principal strategy such as combinatorial chemistry computer modelling and calculation supramolecular synthesis and supramolecular phase formation function in nanoscale stimula responsive study intelligent materials creation was developed for each type of substances. Synthetical details and identification are outside of this proceeding. Report Documentation Page Form Approved

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تاریخ انتشار 2005