Hollow structures containing pockets and pores formed by oligopeptides and proteins are involved in numerous biological processes. Except for a small number of hollows associated with secondary structures, most voids in nature are associated with tertiary and quaternary structures of proteins. One of the most important aspect of natural hollow structures is the exquisite complementarity between their sizes and functions and those of the corresponding guest molecules, process, and reactions. With their complementarity, natural cavities and pores provide microenviroments that lead to a specific binding, catalysis, transportation, and other functions. Since the discovery of crown ether, many macrocycles have been created as host for various guests. The majority of synthetic macrocycles and their acyclic analogs have flexible backbones and thus collapsible cavities. Looking to the example by nature pore-, or cavity-containing secondary structures, work described in this paper stemmed from the development of synthetic peptides containing any cyclic residues insert in well-defined positions of the main chain. This cyclic unit immobilize the curvature into the corresponding backbones, leads an enforced helical (or ring with cyclic peptides) conformation. As a result, a variety of reliably folded, modifiable scaffold can now be constructed. The well-defined crescent helical conformation contain non collassable internal cavities having multiple, introverted amide bonds. Changing the backbone curvature by tuning the cyclic unit (geometry and/or position) leads to crescents ring dimension or helical with cavities of tunable sizes. We synthesized a series of molecules inserting cyclic units in well-defined position obtaining the designed, natural-like hollow structure. The computational and spectroscopic integrated study of these models allowed us to identify different new structures that will be discussed. [1] Fenude E.., Roggio A.M SardiniaChem2006 Giornata di Studio Dedicata alla Chimica Organica delle Molecole Biologicamente Attive, Cagliari 31 Maggio 2006 [2] E. Fenude, S. Dedola, M. Fais VII Convegno "Complex Systems: structure, properties, reactivity and dynamics" Alghero, 2005 [3] Navarro, E.; Fenude, E.; Celda, B. Biopolymers, 73, 2004,229-241 [4] Saviano, M.; .Zaccaria, L.; Lombardi,A.; Pedone,C.; Di Blasio,B.; Sun, X.; Lorenzi,G.P.; J.of Inclusion Phenomena and Molecular Recognition in Chemistry, 1994, 18, p.27-36
Hollow crescent based on backbone-rigidified oligopeptides.
EFenude;
2012
Abstract
Hollow structures containing pockets and pores formed by oligopeptides and proteins are involved in numerous biological processes. Except for a small number of hollows associated with secondary structures, most voids in nature are associated with tertiary and quaternary structures of proteins. One of the most important aspect of natural hollow structures is the exquisite complementarity between their sizes and functions and those of the corresponding guest molecules, process, and reactions. With their complementarity, natural cavities and pores provide microenviroments that lead to a specific binding, catalysis, transportation, and other functions. Since the discovery of crown ether, many macrocycles have been created as host for various guests. The majority of synthetic macrocycles and their acyclic analogs have flexible backbones and thus collapsible cavities. Looking to the example by nature pore-, or cavity-containing secondary structures, work described in this paper stemmed from the development of synthetic peptides containing any cyclic residues insert in well-defined positions of the main chain. This cyclic unit immobilize the curvature into the corresponding backbones, leads an enforced helical (or ring with cyclic peptides) conformation. As a result, a variety of reliably folded, modifiable scaffold can now be constructed. The well-defined crescent helical conformation contain non collassable internal cavities having multiple, introverted amide bonds. Changing the backbone curvature by tuning the cyclic unit (geometry and/or position) leads to crescents ring dimension or helical with cavities of tunable sizes. We synthesized a series of molecules inserting cyclic units in well-defined position obtaining the designed, natural-like hollow structure. The computational and spectroscopic integrated study of these models allowed us to identify different new structures that will be discussed. [1] Fenude E.., Roggio A.M SardiniaChem2006 Giornata di Studio Dedicata alla Chimica Organica delle Molecole Biologicamente Attive, Cagliari 31 Maggio 2006 [2] E. Fenude, S. Dedola, M. Fais VII Convegno "Complex Systems: structure, properties, reactivity and dynamics" Alghero, 2005 [3] Navarro, E.; Fenude, E.; Celda, B. Biopolymers, 73, 2004,229-241 [4] Saviano, M.; .Zaccaria, L.; Lombardi,A.; Pedone,C.; Di Blasio,B.; Sun, X.; Lorenzi,G.P.; J.of Inclusion Phenomena and Molecular Recognition in Chemistry, 1994, 18, p.27-36I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
