Synthesis and micellization of star‐like hyperbranched polymer with poly(ethylene oxide) and poly(ε‐caprolactone) arms

Novel star‐like hyperbranched polymers with amphiphilic arms were synthesized via three steps. Hyperbranched poly(amido amine)s containing secondary amine and hydroxyl groups were successfully synthesized via Michael addition polymerization of triacrylamide (TT) and 3‐amino‐1,2‐propanediol (APD) with feed molar ratio of 1:2. ¹H, ¹³C, and HSQC NMR techniques were used to clarify polymerization mechanism and the structures of the resultant hyperbranched polymers. Methoxyl poly(ethylene oxide) acrylate (A‐MPEO) and carboxylic acid‐terminated poly(ε‐caprolactone) (PCL) were sequentially reacted with secondary amine and hydroxyl group, and the core–shell structures with poly(1TT‐2APD) as core and two distinguishing polymer chains, PEO and PCL, as shell were constructed. The star‐like hyperbranched polymers have different sizes in dimethyl sulfonate, chloroform, and deionized water, which were characterized by DLS and ¹H NMR. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1388–1401, 2008     

Redox,ionic strength,and pH sensitive supramolecular polymer assemblies

Formation of micelle‐type assembly from supramolecular complexation of a surfactant and an oppositely charged homopolymer is demonstrated. The lower CAC observed for these assemblies suggest that the electrostatic interaction provides an amphiphilic homopolymer‐like structure. The stimulus‐induced disassembly of these supramolecular structures has been accomplished with variations in redox characteristics, ionic strength, and pH of the medium. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1052–1060, 2009     

Synthesis,self‐assembly and drug‐loading capacity of well‐defined drug‐conjugated amphiphilic A2B2 type miktoarm star copolymers based on poly(ε‐caprolactone) and poly(ethylene glycol)

Well‐defined drug‐conjugated amphiphilic A₂B₂ miktoarm star copolymers [(PCL)₂‐(PEG)₂‐D] were prepared by the combination of controlled ring‐opening polymerization (CROP) and “click” reaction strategy. First, bromide functionalized poly(ε‐caprolactone) (PCL‐Br) with double hydroxyl end groups was synthesized by the CROP of ε‐caprolactone using 2,2‐bis(bromomethyl)propane‐1,3‐diol as a difunctional initiator in the presence of Sn(Oct)₂ at 110 °C. Next, the bromide groups of PCL‐Br were quantitatively converted to azide form by NaN₃ to give PCL‐N₃. Subsequently, the end hydroxyl groups of PCL‐N₃ were capped with ibuprofen as a model drug at room temperature. Finally, copper(I)‐catalyzed cycloaddition reaction between ibuprofen‐conjugated PCL‐N₃ and slightly excess alkyne‐terminated poly(ethylene glycol) (A‐PEG) led to ibuprofen‐conjugated A₂B₂ miktoarm star copolymer [(PCL)₂‐(PEG)₂‐D]. The excess A‐PEG was removed by dialysis. ¹H NMR, FTIR and SEC analyzes confirmed the expected miktoarm star architecture. These amphiphilic miktoarm star copolymers could self‐assemble into multimorphological aggregates in aqueous solution, which were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In addition, the drug‐loading capacity of these drug‐conjugated miktoarm star copolymers as well as their nondrug‐conjugated analogs were also investigated in detail. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

A new water‐soluble branched poly(ethylene imine) derivative having hydrolyzable imidazolidine moieties and its application to long‐lasting release of aldehyde

A new water‐soluble poly(ethylene imine)‐derivative having imidazolidine moieties was developed. With using branched poly(ethylene imine) (BPEI) as a precursor, it was modified by Michael addition reaction of its primary amino group to an acrylate having poly(ethylene glycol) (PEG) chain. The modified BPEI was reacted with octanal to give the corresponding BPEI derivative having octanal‐derived imidazolidine moieties. The obtained polymer inherited the high hydrophilicity of the attached PEG chains to allow hydrolysis of the imidazolidine moieties under homogeneous conditions in aqueous media, leading to long‐lasting release of octanal. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis of linear and hyperbranched sugar‐grafted polysiloxanes using N‐hydroxysuccinimide‐activated esters

A straightforward method for the preparation of polysiloxanes grafted with carbohydrate side groups is described. Two kinds of backbones have been functionalized, namely one‐dimensional, linear polysiloxanes, and hyperbranched poly(siloxysilane)s based on cyclotetrasiloxanes. The method enables us to keep a good integrity of the polysiloxane backbone. The introduction of intermediate activated esters as side groups on the polysiloxane backbone ensures a complete homogeneity of the reaction medium during sugar grafting in dimethyl sulfoxide, and consequently an easy grafting with the unprotected amino sugar. Solubility of the resulting polysiloxanes has been tested in various solvents. The sugar‐grafted polysiloxanes are good candidates for applications such as silicone formulations, hydrophilic silicone elastomers, interactions with metallic nanoparticles, and suspension stabilization, or as starting point for the design of more complex polysiloxanes for molecular recognition. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3607–3618     

Versatile self-assembled hybrid systems with exotic structures and unique functions

In this review article, we describe recent progress about exotic self-assembled systems with various dimensions including biomolecules, supramolecules, unique hydrophobic amphiphiles, polymers, nano-clusters, and colloidal particles. Construction of robust biomolecular assemblies with exotic structures, such as ring and hollow capsule, is achieved by rational designs of symmetric biomolecular conjugates. In addition, we comprehensively summarized leading-edge topics on optical/topological properties of self-assembled hybrid systems, such as circularly polarized luminescence or structural color. The preparation of colloidal amorphous array with photonic band gap-induced angle-independent structural color is also achieved in consideration of the following situations: i) two-body sphere–sphere potential, ii) disorder packing using different sizes of colloidal particles, and iii) softness of colloidal particles. Lastly, we demonstrated useful utilizations of exotic self-assembled objects. Flakelike microparticles were transcribed into various nano-flake metals and applied as temperature indicator for the local heating of an addictive. All findings described here show meaningful hybrid strategies in self-assembly techniques and their functionalization as well as materialization.