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(CHCMe2Ph)(NAr)(OR)(2)] with OR=OCMe3, OCMeC(CF3)(2); Ar=2,6-iPr(2)C(6)H(3), 2,6Me(2)C(6)H(3)- The synthetic strategy is based on the polymerization of norbornene and its derivatives affording diand 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(CH2CH2O)(n)Ms, Ms= MeSO2] 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.