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Bibliografia
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2. Hyde, S.; Anderson, S.; Larsson, K.; Blum, Z.; Landh, T.; Lidin, S.; Ninham, B.W. "The Language of Shape" Elsevier: Amsterdam, 1997.
3. Lipowsky, R.; Sackman E. "Structure and Dynamics of Membranes" North-Holland: Amsterdam, 1995.
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9. Reactions and Synthesis in Surfactant Systems; J. Texter Ed.: Dekker, New York, 2001.
10. Zhang S.G., Emerging biological materials through molecular self-assembly, Biotechnology Advances 20 (5-6): 321 DEC 2002.
11. Dosch H. "Some general aspects of confinement in nanomaterials" Appl. Surf. Sci. 2001, 182, 192.
12. Bogunia-Kubik, K.; Sugisaka M. "From molecular biology to nanotechnology and nanomedicine" Biosystems 2002, 65, 123.
13. Allen J.W. et al. "Future probes in materials science" Physica B: Condensed Matter 2002, 318, 12.
14. Robinson, B. H., Ed, Self-assembly, IOS Press: Amsterdam, 2003
15. Alfridsson, M.; Ninham, B.W.; Wall S. "Role of Co-Ion Specificity and Dissolved Atmospheric Gas in Colloid Interaction" Langmuir 2000, 16, 10087.
16. Branden, C.; Tooze, J. "Introduction to Protein Structure" Garland Publ: New York, 1991. Lilley D. M.J. ed., DNA-protein: Structural Interactions" (Frontiers in Molecular Biology Series), Oxford University Press: Oxford (1995).
17. Kyle, R. A.; Grateau, G. "Amyloid and Amyloidosis", CRC Press (2004)
18. Song, X. "The role of anisotropic interactions in protein crystallization", Phys. Rev. E 2002, 66, 011906.
19. Lonetti, B.; Fratini, E.; Chen, S. H.; Baglioni, P. (2004). "Viscoelastic and small angle neutron scattering studies of concentrated protein solutions" Physical Chemistry Chemical Physics, 6, 1388.
20. Baglioni, P.; Fratini, E.; Lonetti, B.; Chen, S. H. (2004). "Gelation in Cytochrome C concentrated solutions near the isoelectric point: the anion role" Current Opinion In Colloid & Interface Science, 9, 38.
21. Baglioni, P.; Fratini, E.; Lonetti, B.; Chen, S. H. (2004). Structural arrest in concentrated cytochrome C solutions: the effect of pH and salts. Journal Of Physics-Condensed Matter, 16, S5003. 22. Randazzo, D.; Berti, D.; Briganti, F.; Baglioni, P.; Scozzafava, A.; Di Gennaro, P.; Galli, E.; Bestetti, G. "Efficient polycyclic aromatic hydrocarbons dihydroxylation in direct micellar systems" Biotechnol. Bioeng. 2001, 74, 240.
23. Stefan, A.; Palazzo, G.; Ceglie, A.; Panzavolta, E.; Hochkoeppler, A. Water-in-Oil Macroemulsions Sustain Long-Term Viability of Microbial cells in organic solvents" Biotechnol. Bioeng. 2003, 81, 323.
24. Lo Nostro, P.; Fratoni, L.; Baglioni, P. "Modification of a Cellulosic Fabric with Cyclodextrin for Textile Finishing applications" J. Inclusion Phenomena Macrocyclic Chemistry (2003).
25. Mele, S.; Murgia, S.; Caboi, F.; Monduzzi, M. (2004). Biocompatible lipid formulations: Phase diagrams and microstructures from Optical Microscopy and multinuclear NMR Spectroscopy. Langmuir, 20, 5241.
26. Caboi, F.; Amico, G.S.; Pitzalis, P.; Monduzzi, M.; Nylander, T.; Larsson, K. (2001). Addition of Hydrophilic and Lipophilic Compounds of Biological Relevance to the Monoolein/Water System. I - Phase Behavior by NMR and SAXS. Chemistry And Physics Of Lipids, 109, 47.
27. Angelico, R.; Ceglie, A.; Colafemmina, G.; Lopez, F.; Murgia, S.; Olsson, U.; Palazzo, G. (2005). Biocompatible lecithin organogels: structure and phase equilibria. Langmuir, 21, 140.
28. Carretti, E.; Dei, L.; Baglioni, P. (2004). Aqueous polyacrylic acid based gels: Physicochemical properties and applications in cultural heritage conservation. Progress In Collodi & Polymer Science, 123, 280.
29. Lo Nostro, P.; Ceccato, M.; Baglioni, P. "Polysaccharide Applications. Cosmetics and Pharmaceuticals", ACS Symposium Series 737, Ed. M.A. El-Nokaly and H.A. Soini, Washington DC, 1999, 46.
30. Colafemmina, G.; Palazzo, G.; Ceglie, A.; Ambrosone, L.; Cinelli, G.; Di Lorenzo, V. "Restricted diffusion: an effective tool to investigate food emulsions", Progr. Colloid Pol. Sci. 2002, 120, 2323.
31. Bonini, M.; Bardi, U.; Berti, D.; Neto, C.; Baglioni, P. - A New Way to Prepare Nanoparticles and Nanostructured Materials: Flame Spraying of Microemulsions. J. Phys. Chem. B 2002.
32. Bonini, M.; Wiedenmann, A.; Baglioni, P. (2004). Synthesis and characterization of surfactant and silica-coated cobalt ferrite nanoparticles. Physica A-Statistical Mechanics And Its Applications. 339, 86.
33. Ariga, K.; Kunitake, T. - Molecular recognition at air-water and related interfaces: Complementary hydrogen bonding and multi-site interaction. Acc. Chem. Res. 1998, 31, 371.
34. Marchi-Artzner, V.; Lehn, J.M.; Kunitake, T. - Specific Adhesion and Lipid Exchange between Complementary Vesicle and Supported or Langmuir Film. Langmuir 1998, 14, 6470.
35. Marchi-Artzner, V.; et al. - Selective adhesion, lipid exchange and membrane-fusion processes between vesicles of various sizes bearing complementary molecular recognition groups. Chem. Phys. Chem. 2001, 2, 367.
36. Berti, D.; Franchi, L.; Baglioni, P.; Luisi, P.L. - Molecular recognition in monolayers. Complementary base pairing in dioleoylphosphatidyl derivatives of adenosine, uridine, and cytidine. Langmuir 1997, 13, 3438.
37. Berti, D.; Baglioni, P.; Bonaccio, S.; Barsacchi-Bo, G.; Luisi, P.L. - Base complementarity and nucleoside recognition in phosphatidylnucleoside vesicles. J. Phys. Chem. B 1998, 102, 303.
38. Berti, D.; Pini, F.; Baglioni, P.; Teixeira, J. - Micellar Aggregates from Short Chain Phospholiponucleosides: a SANS study. J. Phys. Chem. B , 1999, 103, 1738.
39. Berti, D.; Barbaro, P.; Bucci, I.; Baglioni, P. - Molecular recognition through H-bonding in micelles formed by dioctanoylphosphatidyl nucleosides. J. Phys. Chem. B 1999, 103, 4916.
40. Berti, D.; Keiderling, U.; Baglioni, P. - Supramolecular structures formed by Phospholiponucleosides, in. In Lipid and Lipid Polymer Systems. Edited by Lindman B: Springer Verlag; Progr. Colloid Polym. Sci. 2002, 120, 64.
41. Berti, D.; Fratini, E.; Dante, S.; Hauss, T.; Baglioni, P. - A structural study of Lamellar Phases formed by Nucleoside lipids. Applied Physics A, 2002, 74, S522.
42. Baldelli-Bombelli, F.; Berti, D.; Keiderling, U.; Baglioni, P. - Giant Polymerlike Micelles Formed By Nucleoside-functionalized lipids, J.Phys.Chem. B, 2002, 106, 11613.
43. Barthelemy, P.; et al - Chem. Commun., 2005, 1261, 126.
44. Moreau, et al. - Supramolecular Assemblies of Nucleoside Phosphocholine Amphiphiles, J. Am. Chem. Soc.; 2004;126(24), 7533.
45. Vernille, J. P.; Kovell, L. C.; Schneider, J. W. - Peptide Nucleic Acid (PNA) Amphiphiles: Synthesis, Self-Assembly, and Duplex Stability, Bioconjugate Chem., 2004; 20(6); 1776.
46. Marques, B. F.; Schneider, J. W.; Sequence-Specific Binding of DNA to Liposomes Containing Di-Alkyl Peptide Nucleic Acid (PNA) Amphiphiles Langmuir; 2005; 21(6); 2488.
47. Shimizu T et al. Internucleobase-interaction-directed self-assembly of nanofibers from homo- and heteroditopic 1,omega-nucleobase bolaamphiphiles. J. Am. Chem. Soc. 2001, 123, 5947.
48. Iwaura R et al. Spontaneous Fiber Formation and Hydrogelation of Nucleotide Bolamphiphiles. Chem. Mater. 2002, 14, 3047.
Keywords
COLLOIDS, SELF-ASSEMBLIES, BIO-SURFACTANTS SELF-ASSEMBLIES, MICELLES, VESICLES, MICROEMULSIONS, SMALL ANGLE NEUTRON SCATTERING, LIGHT SCATTERING, NUCLEOLIPIDS SYNTHESIS

Self-assembling Nanosystems with DNA/RNA-like Addressability

Università degli Studi di Firenze
Abstract
Non-covalent strategies are a powerful tool for the preparation of new nanomaterials through a “bottom-up” approach. Self-assembled systems, where complex functional structures are generated by assembling a group of interlocking parts, have gained a prominent and ever increasing role. Their advantage over conventional covalent molecular architectures in bottom-up design lies in the ease of preparation and in their intrinsically stimuli-responsive character.
The general phase behavior of complex fluids composed of amphiphilic self-assemblies is univocally set, rather than by details of the interparticle forces, by elemental features of the interaction potential such as its range, strength, and attraction/repulsion balance. Conversely in bio-molecular recognition studies, the emphasis is rather laid on local, stereo-specific forces.
This project aims at stepping towards a conceptual unification of the approach typical of Soft Matter Science where supramolecular cooperative effects are the driving force leading to self-association, and bio-molecular recognition.

To address the above issues, sequential research objectives will be pursued:

1) Molecular design of tailored amphiphiles, where chemical information units are embedded in a hydrophobic assembler; following the research line pioneered by one of the applicant units, surfactants with nucleic functionalities (nucleolipids) will be synthesized; the synthetic scheme that will be set >>>

Principal Investigator
Piero Baglioni Università degli Studi di FIRENZE
Research Objectives
Aim of this proposal is a detailed understanding of self-assembly and functional properties of a novel class of systems combining both the cooperative self-assembly properties of amphiphilic molecules and specific molecular recognition features characterizing biological macromolecules.
This investigation will proceed through the following objectives:

1) Tailored synthesis of a class of novel amphiphilic molecules cointaining nucleic information units: phospholiponucleosides (PLNs), cationic and zwitterionic nucleolipids with several hydrophobic skeletons. The flexibility in molecular design, will allow tuning their interactions, self-organizing properties, overall phase behaviour, and functional operation. Aim of this part will be the build-up of a chemical platform that will be combinatorially used in step 2 to investigate their phase behavior.

2) Search for interplay between molecular recognition (selective and specific interaction between two chemical units) and self-assembling properties. Aim of this part will be a detailed structural and dynamic characterization performed with state of the art techniques. Particular attention will be devoted to highlight how molecular specificity affects properties on the mesoscopic scale in for different surfactant phases:
2a) Globular micelles and particle supported amphiphilic films
2b) Wormlike micellar phases and o/w micellar phases
2c) Reverse phases

3 >>>

Timescale
24 months
National and international background
In the last decade inherently multidisciplinary area of Colloid Science has been "restyled", integrating areas of research and development at the interface between Biology, Chemistry and Physics under the title Nanoscience. [1-14] It has done so and moved to center stage: Nanosciences are widely considered as having enormous potential to bring benefits in areas as diverse as biotechnologies, drug development, water decontamination, information and communication technologies, and the production of stronger, lighter and "intelligent" materials for a variety of applications.
The merging of different research areas consistently improved the understanding of the incredibly rich and complex nature of biological processes that are deeply rooted into the synergy of two fundamental kinds of spontaneously-occurring processes: specific molecular recognition and self-association.
On the one hand, unique molecular design, stereo-specificity, "vectorial" interactions are the core structural features of proteins and nucleic acids, making them so much "smart" macromolecules. Local molecular recognition is strongly intertwined with large scale molecular organization, since it often requires self-assembled structure as a compartmentalized host medium, and also because leads to large-scale self-association in mesoscopic structures[14].
Although the last two decades have seen unprecedented advancements in our understanding of both >>>