Spontaneous formation of polypeptides in the interfacial thin films of amphiphilic amino acid esters: acceleration of the polycondensation and control of the structure of resultant polymers.
For the purpose of elucidating the effects of molecular arrangements on the reaction rates and the structure of products, polycondensation of long-chain esters of alpha-amino acids in the monolayer on the water surface and the LB multilayers deposited on CaF2 plates were investigated by monitoring changes of the IR spectra. Spontaneous formation of the polypeptides occurs in the mono- and multilayers at room temperature without any catalyst. The rates of polycondensation in the monolayers are markedly influenced by the degree of molecular packing. Maximum polymerizability is obtained in the vicinity of the transition region from expanded to condensed films. The rates of polycondensation in the LB films are much higher than those in the bulk solids and the molten states. The polycondensation seems to be accelerated by regular arrangements of the monomer molecules in the LB films, where the functional groups are concentrated and situated more effectively for the reaction than in the bulk states. However, the polycondensation rates in the LB films are considerably slower when compared with those in the monolayers on the water surface kept at the optimum area or surface pressure, because the molecules in the LB films deposited under high compression are packed more closely than the optimum condition. Thus, suitably close packing of the monomer molecules, retaining a particular orientation together with some conformational freedom in the monolayer, is most favorable for the polycondensation. Two probable mechanisms for the polycondensation in the Y-type multilayers have been proposed. In the assembly of head-to-head double layers of the monomer molecules, the interlayer reaction propagates by sewing up the functional groups facing each other in the adjacent layers, and the polypeptide of a helical structure or random coil can be obtained. In contrast, for the alternating assembly of the amino acid ester and non-polymerizable octadecyl acetate, the polycondensation should proceed only in each single layer (intralayer reaction) and the polypeptide of the extended beta-form can be formed. In the case of dioctadecyl glutamate LB films, as well as the monolayer on water, the resultant polypeptide is the comb-like polymer with unreacted long-alkyl ester groups as side chains and abundant in the beta-form, indicating the dominant intralayer reaction. On the other hand, in the Y-type multilayer of the equimolar mixture of dioctadecyl glutamate (with two ester groups) and octadecyl ester of lysine (with two amino groups), both of the intra- and interlayer reactions occur effectively, resulting in a two-dimensional network structure of the polypeptide. In conclusion, not only the rate of polycondensation but also the higher-order structure of the resultant polypeptides can be controlled by organized arrangements of the monomer molecules in the interfacial thin films.
Fukuda
K
K
Department of Chemistry, Faculty of Science, Saitama University, Urawa, Japan.
Shibasaki
Y
Y
Nakahara
H
H
Liu
M H
MH
D000409:Alanine / Q000737:chemistry; D000596:Amino Acids / Q000737:chemistry*; D004952:Esters; D018698:Glutamic Acid / Q000737:chemistry; D005998:Glycine / Q000737:chemistry; D007202:Indicators and Reagents; D007700:Kinetics; D008239:Lysine / Q000737:chemistry; D010455:Peptides / Q000737:chemistry*; D013499:Surface Properties
D000596:Amino Acids; D004952:Esters; D007202:Indicators and Reagents; D010455:Peptides; D018698:Glutamic Acid; D008239:Lysine; D000409:Alanine; D005998:Glycine