Hewen Liu

pH-Responsive Supramolecular Self-Assembly of Well-Defined Zwitterionic ABC Miktoarm Star Terpolymers

We report the first example of the synthesis and pH-responsive supramolecular self-assembly of double hydrophilic ABC miktoarm star terpolymers. Well-defined ABC miktoarm star terpolymers consisting of poly(ethylene glycol), poly(tert-butyl methacrylate), and poly(2-(diethylamino)ethyl methacrylate) arms [PEG(-b-PtBMA)-b-PDEA] were synthesized via the combination of consecutive click reactions and atom transfer radical polymerization (ATRP), starting from a trifunctional core molecule, 1-azido-3-chloro-2-propanol (ACP). The click reaction of monoalkynyl-terminated PEG with an excess of ACP afforded difunctional PEG bearing a chlorine and a secondary hydroxyl moiety at the chain end, PEG113(-Cl)-OH (1). After azidation with NaN3, PEG-based macroinitiator PEG113(-N3)-Br (3) was prepared by the esterification of PEG113(-N3)-OH (2) with 2-bromoisobutyryl bromide and then employed in the ATRP of tert-butyl methacrylate (tBMA). The obtained PEG(-N3)-b-PtBMA copolymers (4) possessed an azido moiety at the diblock junction point. The preparation of PEG(-b-PtBMA)-b-PDEA miktoarm star terpolymers was then achieved via the click reaction of 4 with an excess of monoalkynyl-terminated PDEA. The obtained miktoarm star terpolymers were successfully converted into PEG(-b-PMAA)-b-PDEA, where PMAA is poly(methacrylic acid). In aqueous solution, PEG(-b-PMAA)-b-PDEA zwitterionic ABC miktoarm star terpolymers can self-assemble into three types of micellar aggregates by simply adjusting solution pH at room temperature. Above pH 8, PDEA-core micelles stabilized by PEG/ionized PMAA hybrid coronas were formed due to the insolubility of PDEA block. In the range of pH 5-7, micelles possessing polyion complex cores formed as a result of charge compensation between partially ionized PMAA and partially protonated PDEA sequences. At pH<4, hydrogen bonding interactions between fully protonated PMAA and PEG led to the formation of another type of micellar aggregates possessing hydrogen-bonded complex cores stabilized by protonated PDEA coronas. The fully reversible pH-responsive formation of three types of aggregates were characterized by 1H NMR, dynamic and static laser light scattering (LLS), and transmission electron microscopy (TEM).

Multifunctional Conjugates To Prepare Nucleolar-Targeting CdS Quantum Dots

We used a click reaction to synthesize a bidentate 1,2,3-triazole-based ligand, TA, for use in the preparation of aqueous CdS quantum dots (QDs). TA-conjugated CdS QDs exhibited two fluorescence emission peaks, one at 540 nm arising from CdS nanocrystals and the other at approximately 670 nm arising from TA-CdS QD complexes formed via surface coordination. Coordination between TA and CdS was verified by using X-ray photoelectron (N 1s) spectra as well as Raman and NMR spectra of TA-capped QDs. Electrochemical analysis revealed that the 1,2,3-triazole moities in TA form complexes with the Cd(II) ions. The aqueous QDs protected by TA were very stable at different ionic strengths and over a broad pH range, according to fluorescence analysis. The ethidium bromide exclusion assay demonstrated that the bidentate TA ligand interacts strongly with DNA. Fluorescent micrographs and TEM images of cancer cells stained with TA-capped QDs clearly showed that the TA ligand targeted CdS QDs to the nucleoli of cells. In contrast, thioglycolic acid-capped CdS QDs just stained the cell membranes and could not pass the cell membranes to reach the cell nucleus.

Radical alternating copolymerization: A strategy for hyperbranched materials

Novel hyperbranched polymers were synthesized in a high yield without gelation through the free-radical alternating copolymerization of an AB/B′ (allyloxy maleic acid/maleic anhydride) system, in which group B and monomer B′ both could only alternately polymerize with group A. The arm number of the produced highly branched polymers was equal to the product of the linear chain length and the probability of pendent B groups being growing centers. The molecular weight of these novel hyperbranched polymers increased with increasing initiator concentration and prolonged polymerization times. The AB/B′ system, used as described, provides a new general methodology for highly branched and functional polymers.

Reaction of epoxy resin and hyperbranched polyacids

The condensation reaction between two different epoxy resins and a hyperbranched polyester (MAHP) [poly(allyloxy maleic acid-co-maleic anhydride)] was studied. We compared two kinds of diglycidyl ether bisphenol A type of epoxy resins with different molecular weights, that is, epoxy resin GY240 (M = 365 g/mol) and GT6064 (M = 1540 g/mol) in this reaction. The results showed a marked difference in their reaction pattern in terms of ability to form crosslinked polymer networks with MAHP. For the former low-molecular-weight epoxy resin, no crosslinking could be observed in good solvents such as THF or dioxane within the set of reaction conditions used in this study. Instead, polymers with epoxide functional degrees between 0.34 and 0.5 were formed. By contrast, the latter high-molecular-weight epoxy resin, GT6064, rapidly produced highly crosslinked materials with MAHP under the same reaction conditions. The spherical-shape model of hyperbranched polymer was applied to explain this difference in reaction behavior. Hence, we have postulated that low-molecular-weight epoxy resins such as GY240 are unable to crosslink the comparatively much bigger spherically shaped MAHP molecules. However, using high-molecular-weight epoxy resins greatly enhances the probability of crosslinking in this system. Computer simulations verified the spherical shape and condensed bond density of MAHP in good solvents, and submicron particle analysis showed that the average MAHP particle size was 9 nm in THF. Furthermore, the epoxy-functionalized polyesters were characterized by 1H NMR and FTIR, and the molecular weights and molecular-weight distributions were determined by size-exclusion chromatography.

Hyperbranched polymers with maleic functional groups as radical crosslinkers

The crosslinking performance of the unsaturated hyperbranched polyester poly(allyloxy maleic acid-co-maleic anhydride) (MAHP) was investigated with copolymerizations of three different monomers: styrene, vinyl acetate, and methyl methacrylate. Both styrene and vinyl acetate afforded interpenetrating-polymer-network copolymer gels. The gels exhibited crosslink density gradients through the polymer matrices on a macroscopic level, and density maximums were concentrated around the MAHP moieties. The heterogeneity of the gels is briefly discussed in terms of a modified two-phase model, where one phase consists of an elastic part of low crosslinking density and the other phase consists of an inelastic dendritic part with a highly condensed bond density. Unlike the two-phase model developed by Choquet and Rietsch, the modified two-phase model takes into account that both phases swell in good solvents. Unlike copolymerizations employing styrene or vinyl acetate, the copolymerization of MAHP with methyl methacrylate afforded noncrosslinked starbranched copolymers that consisted of a MAHP core from which long poly(methyl methacrylate) branches were protruding. The different behaviors of the copolymerizations of the three monomers used in this study can rationally be explained by their different reactivity ratios with maleic end groups of MAHP.

Glass-Transition Temperature as a Function of Conversion in Hyperbranched Polymers Obtained by Self-Condensing Vinyl Polymerization

Chain-end free volume theory is extended for studying the glass-transition temperature (T g ) as a function of conversion in hyperbranched polymers. T g is found to have a non-linear inverse relationship to the molecular weight for polymers obtained by self-condensing vinyl polymerization (SCVP). During the monomer conversion process, T g decreases with the increase in molecular weight (P) in the low conversion range, then levels off in the high conversion range.