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Self‐Assembling Structures of Long‐Chain Sugar‐Based Amphiphiles Influenced by the Introduction of Double Bonds
Author(s) -
Jung Jong Hwa,
Do Youngkyu,
Lee YoungA,
Shimizu Toshimi
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200401288
Subject(s) - hydrogen bond , crystallography , intermolecular force , double bond , moiety , bilayer , alkyl , ribbon , materials science , self assembly , supramolecular chemistry , amphiphile , crystal structure , chemistry , stereochemistry , molecule , nanotechnology , polymer chemistry , polymer , copolymer , organic chemistry , membrane , biochemistry , composite material
Abstract Nine phenyl glucoside or galactoside amphiphiles possessing a saturated or unsaturated long alkyl‐chain group as the self‐assembling unit of a highly organized molecular architecture were synthesized. Their self‐assembly properties were investigated by using energy‐filtering TEM (EF‐TEM), SEM, CD, XRD, and FT‐IR techniques. Compound 2 , possessing one cis double bond in the lipophilic portion, exhibited twisted helical fibers, which formed a bilayered structure with a 3.59 nm period, while 3 exhibited helical ribbons and left‐handed nanotubular structures with 150–200 nm inner diameters and a wall thickness of approximately 20 nm. Very interestingly, 4 , possessing three cis double bonds, exhibited a nanotubular structure with an inner diameter of approximately 70 nm and a d spacing value of 4.62 nm. On the other hand, 7 , possessing two trans double bonds in the lipophilic region, exhibited crystal‐ or plate‐like structures, which formed a bilayer structure with a d spacing value of 3.93 nm. These results indicate that the self‐assembly properties are strongly dependent on the type of double bond. Furthermore, 8 and 9 , with the galactopyranose moiety, revealed helical ribbon and well‐defined double helical fiber structures, respectively. These findings support the view that the orientation of the intermolecular hydrogen‐bonding interaction between the sugar moieties plays a critical role in producing the nanotubular structures. According to CD and powder XRD experiments, the relatively strong intermolecular hydrogen‐bonding interaction of the glucopyranoside moiety in 3 and 4 provided a highly ordered chiral packing structure. Even though these compounds formed a weak hydrophobic interaction between lipophilic groups, it led to the formation of the nanotubular structure.