[en] Spin-coating of isolated positively charged macromolecules onto mica in the presence of octylamine was found to be a simple and general method of stretching and aligning the macromolecular chains. The contour length and molar mass for the stretched macromolecules can be directly measured by atomic force microscopy, which makes this method a very useful analytical tool. Moreover, the molecular height is increased by codeposition with octylamine, which drastically improves the molecular resolution and allows even ultrathin polycations to be visualized. The reason for the key role of the octylamine is found in the formation of an ultrathin liquidlike alkylamine film, which reduces the surface energy of mica and weakens the interactions between the surface and the charged macromolecules.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Bocharova, Vera; Leibniz Institute of Polymer Research, Dresden, Germany
Kiriy, Anton; Leibniz Institute of Polymer Research, Dresden, Germany
Stamm, Manfred; Leibniz Institute of Polymer Research, Dresden, Germany
Stoffelbach, François; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Simple method for the stretching and alignment of single adsorbed synthetic polycations
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique F.R.S.-FNRS - Fonds de la Recherche Scientifique DFG - Deutsche Forschungsgemeinschaftand ESF - European Science Foundation
a) T.T. Perkins, D. E. Smith, S. Chu, Science 1997, 276, 2016;
b) J.T. Finer, R. M. Simmons, J. A. Spudich, Nature 1994, 368, 113.
S. S. Sheiko, M. Möller, Chem. Rev. 2001, 101, 4099.
S.-W. Chung, D. S. Ginger, M. W. Morales, Z. Zhang, V. Chandrasekhar, M. A. Ratner, C. A. Mirkin, Small 2005, 1, 64.
G. Maubach, D. Bom, A. Csaki, W. Fritzsche, Small 2005, 1, 619.
V. Bocharova, A. Kiriy, H. Vinzelberg, I. Mönch, M. Stamm, Angew. Chem. 2005, 117, 6549;
Angew. Chem. Int Ed. 2005, 44, 6391.
N. Severin, J. Barner, A. A. Kalachev, J. P. Rabe, Nano Lett. 2004, 4, 577.
H. Dautzenberg, W. Jaeger, B. P. J. Kotz, C. Seidel, D. Stscherbina, Polyelectroytes: Formation, Characterization and Application, Cart Hanser, Munich, 1994, pp. 166-242.
L. Shu, A. D. Schlüter, C. Ecker, N. Severin, J. P. Rabe, Angew. Chem. 2001, 113, 4802;
Angew. Chem. Int Ed. 2001, 40, 4666.
J. J. L. M. Comelissen, J. J. J. M. Donners, G. Metselaar, R. de Gelder, W. S. Graswinckel, A. E. Rowan, N. A. J. M. Sommerdijk, R. J. M. Nolte, Science 2001, 293, 676.
a) S. Minko, A. Kiriy, G. Gorodyska, M. Stamm, J. Am. Chem. Soc. 2002, 124, 3218;
b) L. J. Kirwan, G. Papastavrou, M. Borkovec, S. H. Behrens, Nano Lett. 2004, 4, 149.
J. Kumaki, T. Hashimoto, J. Am. Chem. Soc. 2003, 125, 4907.
In some cases single-polymer molecules can be detected as bumps in collapsed form due to sufficiently large thickness of the molecular globules: M. Gallyamov, A. R. Khokhlov, M. Möller, Macromol. Rapid Commun. 2005, 26, 456.
a) A. Kiriy, S. Minko, A. Gorodyska, M. Stamm, W. Jaeger, Nano Lett. 2002, 2, 881;
b) A. Kiriy, A. Gorodyska, S. Minko, C. Tsitsilianis, W. Jaeger, M. Stamm, J. Am. Chem. Soc. 2003, 125, 11202.
N. Crampton, W. A. Bonass, J. Kirkham, N. H. Thomson, Langmuir 2005, 21, 7884.
H. Nakao, M. Gad, S. Sugiyama, K. Otobe, T. Ohtani, J. Am. Chem. Soc. 2003, 125, 7162.
M. B. J. Otten, C. Ecker, G. A. Metselaar, A. E. Rowan, R. J. M. Nolte, P. Samori, J. P. Rabe, ChemPhysChem 2004, 5, 128.
N. Severin, J. P. Rabe, D. G. Kurth, J. Am. Chem. Soc. 2004, 126, 3696.
P. Samorí, J.J.J.M. Donners, N. Severin, M. B. J. Otten, J. P. Rabe, R. J. M. Nolte, N. A. J. M. Sommerdijk, Langmuir 2004, 20, 8955.
The molecular weight of the samples was determined by SEC of the corresponding parent uncharged precursors in THF for P2VP and in THF/triethylamine (95:5) for PMADAME, using polystyrene standards.
Detailed synthesis and characterization of the PMADAME-Py will be published elsewhere.
The Austin Model (AMI) is implemented in the HYPRCHEM package (version 6.03).
T. A. Betley, B. Holl, B. Orr, D. R. Swanson, D. A. Tomalia, J. R. Baker, Langmuir 2001, 17, 2768.
T. E. Dukette, M. E. Mackay, B. Van Horn, K. L. Wooley, E. Drockenmuller, M. Malkoch, C. J. Hawker, Nano Lett. 2005, 5, 1704.
Recently Kasumov et al. demonstrated that the observed variations of the molecular thickness of ds-DNA determined by TM-AFM are due to differences in the "molecule-substrate" interactions, which result in different compressing deformations of the molecule rather than because of the tip-induced deformations. Thus, TM-AFM reflects "real' conformations of the ds-DNA if the highest possible value of the amplitude set point is applied: A.Y. Kasumov, D. V. Klinov, P.-E. Roche, S. Gueron, H. Bouchiat, Appl. Phys. Lett. 2004, 84, 1007.
J. J. Benitez, D. F. Ogletree, M. Salmeron, Langmuir 2003, 19, 3276.
An increase in the molecular thickness for chains swollen by vapors of a "good" solvent has also been reported: W. Zhuang, C. Ecker, G. A. Metselaar, A. E. Rowan, R. J. M. Nolle, P. Samorí, J. P. Rabe, Macromolecules 2005, 38, 473.
Here "local" conformations are conformations of macromolecular repeat units.
The term "helical conformation" does not reflect perfect helical order, such as in peptides or in ds-DNA, but only emphasizes that a considerable fraction of the macromolecular repeat units are organized in such a way that emanating adjacent side groups form a dihedral angle of about 90.
It has been demonstrated that a hydrophilic tip is attracted to hydrophilic surfaces more strongly than to hydrophobic ones: S. J. T. Van Noort, K. O. Van der Werf, B. G. De Grooth, N. F. Van Hulst, J. Greve, Ultramicroscopy 1997, 69, 117.
B. Dong, M. Krutschke, X. Zhang, L. Chi, H. Fuchs, Small 2005, 1, 520.