A QCM study of strong carbohydrate-carbohydrate interactions of glycopolymers carrying mannosides on substrates.

Carbohydrates on cell surfaces are known to interact not only with lectins but also with other carbohydrates; the latter process is known as a carbohydrate-carbohydrate interaction. Such interactions are observed in complex oligosaccharides. It would be surprising if these interactions were observed in simple monosaccharides of mannose. In this study, the interaction between glycopolymers carrying monosaccharides of mannose was quantitatively investigated by quartz crystal microbalance measurements. We measured the interactions with glycopolymers carrying mannose, galactose and glucose. Surprisingly, the interaction between the glycopolymers and mannose was much stronger than that between other saccharides.

Aggregation of a double hydrophilic block glycopolymer: the effect of block polymer ratio.

Double hydrophilic block glycopolymers (DHBGs) composed of glycopolymers and polyethylene glycol (PEG) aggregate in aqueous solution. However, there are no guidelines to direct and design DHBG aggregation. Herein, we investigated the effect of the ratio of glycopolymer length to PEG length on the structure, and report that structure size could be influenced by the block polymer ratio. Nine kinds of DHBG with different glycopolymers and PEG lengths were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The aggregation capability of DHBG was investigated by transmission electron microscopy (TEM) and dynamic light scattering (DLS). In all cases, the DHBGs formed the spherical structures, even when the PEG and glycopolymer lengths were quite different. The size of the structure was controlled by the ratio of the PEG length to the glycopolymer length. The aggregation of the DHBGs was induced by hydrogen bonding between the sugar moieties. The aggregation of the DHBG was affected by temperature and concentration.

Replacing Cu(II)Br2 with Me6-TREN in Biphasic Cu(0)/TREN Catalyzed SET-LRP Reveals the Mixed-Ligand Effect.

The mixed-ligand system consisting of tris(2-aminoethyl)amine (TREN) and tris(2-dimethylaminoethyl)amine (Me6-TREN) during the Cu(0) wire-catalyzed single electron transfer-living radical polymerization (SET-LRP) of methyl acrylate (MA) in "programmed" biphasic mixtures of the dipolar aprotic solvents NMP, DMF, and DMAc with H2O is reported. Kinetic and chain end analysis studies by NMR and MALDI-TOF before and after thio-bromo "click" reaction demonstrated that Me6-TREN complements and makes the less expensive TREN a very efficient ligand in the absence of externally added Cu(II)Br2. Statistical analysis of the kinetic data together with control experiments demonstrated that this mixed-ligand effect enhanced the apparent rate constant of propagation, monomer conversion, and molecular weight control. The most efficient effect was observed at a 1/1 molar ratio between these two ligands, suggesting that in addition to a fast exchange between the two ligands, a new single dynamic ligand generated by hydrogen bonding may be responsible for the mixed ligand observed.

Self-Assembly of a Double Hydrophilic Block Glycopolymer and the Investigation of Its Mechanism.

We report the self-assembly of a double hydrophilic block glycopolymer (DHBG) via hydrogen bonding and coordinate bonding. This DHBG, composed of poly(ethylene)glycol (PEG) and glycopolymer, self-assembled into a well-defined structure. The DHBG was prepared through the controlled radical polymerization of trimethylsilyl-protected propargyl methacrylate using a PEG-based reversible addition-fragmentation chain transfer reagent, followed by sugar conjugation using click chemistry. The DHBG self-assembly capability was investigated by transmission electron microscopy and dynamic light scattering. Interestingly, the DHBG self-assembled into a spherical structure in aqueous solution. Hydrogen bonding and coordinate bonding with Ca2+ were identified as the driving forces for self-assembly.