Precise synthesis of poly(macromonomer)s containing sugars by repetitive ROMP and their attachments to poly(ethylene glycol): synthesis, TEM analysis and their properties as amphiphilic block fragments.
Various poly(macromonomer)s (PMMs) have been prepared by a repeating ring opening metathesis polymerization (ROMP) technique using the well-defined molybdenum initiators of the type, [Mo(CHCMe(2)Ph)(NAr)(OR)(2)] with OR=OCMe(3), OCMeC(CF(3))(2); Ar=2,6-iPr(2)C(6)H(3), 2,6-Me(2)C(6)H(3). The synthetic strategy is based on the polymerization of norbornene and its derivatives affording di- and triblock side chains bearing sugars (mannose, galactose, glucose etc.), linked via O- (ester), and glycosidase resistant C- (isoxazoline) glycosides. The efficient placement of norbornene units on the side chain termini and their conversion into PMMs, facilitated by the Mo alkylidenes, proceeded in a living manner with the quantitative initiation. The methodology was applied to prepare poly(macromonomer)-graft-PEG [PEG: poly(ethylene glycol)], by the attachment of a pseudo phenol terminus on the PMM main chain to PEG-Ms(2) [MsO(CH(2)CH(2)O)(n)Ms, Ms=MeSO(2)] using a "grafting to" approach. Removal of the acetal protecting groups from the sugar coating of a variety of supramolecular structures including PMMs, linear amphiphilic block copolymers (ABC) and a PMM-graft-PEGby using trifluroacetic acid/water (9:1), and suspension in water, prompted the spontaneous formation of spherical architectures by self-assembly of the amphiphilic PMMs as observed by transmission electron microscopy (TEM). The ability to uptake the hydrophobic dye (Nile Red) into the micellar cores of a variety of amphiphilic polymeric fragments is a significant step towards the production of sugar-coated nanospheres for cell-targeting biomimetic applications.
Murphy
James J
JJ
Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, Nara 630-0101, Japan.
Furusho
Hirotoshi
H
Paton
R Michael
RM
Nomura
Kotohiro
K
D002241:Carbohydrates / Q000737:chemistry*; D008823:Micelles; D046529:Microscopy, Electron, Transmission; D008968:Molecular Conformation; D009636:Norbornanes / Q000138:chemical synthesis* / Q000737:chemistry; D010078:Oxazines / Q000737:chemistry; D010316:Particle Size; D011092:Polyethylene Glycols / Q000737:chemistry*; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013501:Surface-Active Agents / Q000138:chemical synthesis / Q000737:chemistry
D002241:Carbohydrates; D008823:Micelles; D009636:Norbornanes; D010078:Oxazines; D011108:Polymers; D013501:Surface-Active Agents; D011092:Polyethylene Glycols; C044808:nile red