title: Self-assembled nanogels of cholesteryl-modified polysaccharides: effect of the polysaccharide structure on their association characteristics in the dilute and semidilute regimes.
abstract: The assembly of cholesteryl derivatives of the highly branched polysaccharide mannan Mw = (5.2 x 104 g/mol) in dilute aqueous solution was investigated by 1H nuclear magnetic resonance (NMR) spectroscopy, size-exclusion chromatography coupled with multiangle laser scattering (SEC-MALLS), dynamic light scattering (DLS), atomic force microscopy (AFM), fluorescence quenching, and fluorescence depolarization measurements. In the dilute regime, cholesteryl-bearing mannans (CHM) containing approximately 1 cholesteryl group per 100 mannopyranose units formed nanogels with a hydrodynamic radius (RH) of approximately 20 nm containing approximately 8 macromolecules held together via hydrophobic nanodomains consisting of approximately 9 cholesteryl groups. Their density Phih ( approximately 0.02) was significantly lower than the density ( approximately 0.16) of nanogels formed by a cholesteryl derivative of the linear polysaccharide pullulan (CHP) of identical molar mass and level of cholesteryl substitution. In the semidilute regime, CHM nanogels formed a macrogel network for concentrations higher than 12.5% w/w, whereas CHP nanogels underwent macrogelation only above a threshold concentration of 8.0% w/w, as revealed by oscillatory and steady-shear viscosity measurements. The differences in the solution properties of CHM and CHP reflect differences in their assembly on the molecular level, in particular, the size and number of hydrophobic nanodomains and the hydration level. They are attributed to differences in the mobility of the cholesteryl groups which, itself, can be traced to the fact that in CHM the cholesteryl groups are predominantly linked to short oligomannopyranose branches, whereas in CHP they are linked to the polymer main chain. Our study provides a novel means to nanoengineer polysaccharide nanogels which may find unique biotechnological applications.
authors.affiliation: Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10, Kanda-surugadai, Chiyoda-ku, Tokyo, 101-0062, Japan.
authors.forename: Eri
authors.initials: E
authors.lastname: Akiyama
authors.forename: Nobuyuki
authors.initials: N
authors.lastname: Morimoto
authors.forename: Piotr
authors.initials: P
authors.lastname: Kujawa
authors.forename: Yayoi
authors.initials: Y
authors.lastname: Ozawa
authors.forename: Françoise M
authors.initials: FM
authors.lastname: Winnik
authors.forename: Kazunari
authors.initials: K
authors.lastname: Akiyoshi
mesh_terms: D002784:Cholesterol / Q000737:chemistry*; D005782:Gels; D005936:Glucans / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008351:Mannans / Q000737:chemistry*; D018625:Microscopy, Atomic Force; D053758:Nanoparticles / Q000737:chemistry*; D012996:Solutions; D014783:Viscosity
chemical_list: D005782:Gels; D005936:Glucans; D008351:Mannans; D012996:Solutions; C009109:pullulan; D002784:Cholesterol