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Fmoc or Boc mono-substituted cyclo(L-Lys-L-Lys)s were synthesized via the reaction of lysine cyclic dipeptide with Fmoc N-hydroxysuccinimide este(Fmoc-OSu) and di-tert-butyl dicarbonate[(Boc)2O], respectively. The resulted mono-substituted cyclo(L-Lys-L-Lys)s(2―4) by means of test tube inversion method served as organogelators enabled to form stable thermo-reversible organogels in alcoholic, substituted benzene and chlorinated solvents, with the minimum gelation concentration(MGC) in a range of 1%―4%(mass fraction). The transmission electron microscopy(TEM) and scanning electron microscopy(SEM) observations reveal that these gelators self-assembled into 3D nanofiber, nanoribbon or nanotube network structures. The rheological measurement exhibited that the storage modulus of gels is higher than the loss one, and the complex viscosity is reduced linearly with the increasing of scanning frequency. The fluorescence spectrum of compound 2 in 1,2-dichloroethane and benzene demonstrates that the emission peak of Fmoc at 320 nm has red-shifted and the intensity decreases gradually, while the intensity of the emission peak at 460 nm substantially enhances as a function of concentration, indicating the existence of π-π stacking interactions and the formation of J-type aggregates. Meanwhile, compound 4 self-assembled into nanotubes via the stacking of multiple bilayer membranes. Fmoc and Boc disubstituted cyclo(L-Lys-L-Lys)(3) holds the relatively lower MGC values, showing the stronger gelation ability in most selected organic solvents due to the presence of both Fmoc and Boc groups.

A kind of novel 3-D cross-linked supramolecular structured hydrogels has been fabricated via enzymatic oxidative coupling of polypseudorotaxanes (PPRs) derived from the self-assembly of α-cyclodextrins (α-CDs) with 3-arm p-hydroxyphenylpropionate terminated PEG (3-HPPP) as a macromer by using horseradish peroxidase (HRP)/H2O2 catalytic system. The enzymatic cross-linking of the macomer or PPRs made with a smaller amount of α-CDs was found to be much faster than that by ordinary chemical pathways, showing the promise to be used as the surgical adhesive and sealant which are needed to rapidly function in vivo. The gelation time was highly extended and the gel content was considerably decreased by increasing the α-CDs to macromer feeding molar ratio. Thereby these hydrogels exhibited a decreasing trend in dynamical mechanical properties with increasing the amount of α-CDs in regard to the blank hydrogel made without α-CD addition.

This paper describes a preliminary study on the synthesis of glycopeptide-based triblock copolymers and their aggregate behavior in water. Initially, a polypeptide-based triblock copolymer, poly(L-lysine)-b-poly(tetrahydrofuran)-b-poly(L-lysine) (PLL30-b-PTHF-b-PLL30), was synthesized by the ring-opening polymerization of ɛ-benzyloxycarbonyl-L-lysine N-carboxyanhydride using amine-terminated poly(tetrahydrofuran) as a macroinitiator in the fixed feed ratio, followed by the removal of the protecting group. The resulting copolymer then reacted with a varying amount of D-gluconolactone in the presence of dipropylethylamine to give the corresponding glycopeptide-based copolymers with high yields. This kind of amphiphilic sugar-containing triblock copolymer can self-assemble into nano-sized aggregates in water. The critical aggregation concentration (CAC) was determined in the range of around 10−6 M by fluorescence measurement. The spherical morphologies in 100–150 nm scale were also evidenced by transmission electron microscopy (TEM) measurements. They show potential as carriers for drug controlled delivery and templates for biomimetic mineralization.

A comb-like polyether, poly(3-2-[2-(2-methoxyethoxy)ethoxy]ethoxymethyl-3′-methyloxetane) (PMEOX), was reacted with hexamethylene diisocyanate and extended with butanediol in a one-pot procedure to give novel thermoplastic elastomeric poly(ether urethane)s (TPEUs). The corresponding hybrid solid polymer electrolytes were fabricated through doping a mixture of TPEU and poly(vinylidene fluoride) with three kinds of lithium salts, LiClO4, LiBF4 and lithium trifluoromethanesulfonimide (LiTFSI), and were characterized using differential scanning calorimetry, thermogravimetric analysis and Fourier transform infrared spectroscopy. The ionic conductivity of the resulting polymer electrolytes was then assessed by means of AC impedance measurements, which reached 2.1 × 10−4 S cm−1 at 30 °C and 1.7 × 10−3 S cm−1 at 80 °C when LiTFSI was added at a ratio of O:Li = 20. These values can be further increased to 3.5 × 10−4 S cm−1 at 30 °C and 2.2 × 10−3 S cm−1 at 80 °C by introducing nanosized SiO2 particles into the polymer electrolytes. Copyright © 2006 Society of Chemical Industry

A novel cyclic ether monomer 3-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy-methyl}-3′-methyloxetane (HEMO) was prepared from the reaction of 3-hydroxymethyl-3′-methyloxetane tosylate with triethylene glycol. The corresponding hyperbranched polyether (PHEMO) was synthesized using BF3·Et2O as initiator through cationic ring-opening polymerization. The evidence from 1H and 13C NMR analyses revealed that the hyperbranched structure is constructed by the competition between two chain propagation mechanisms, i.e. active chain end and activated monomer mechanism. The terminal structure of PHEMO with a cyclic fragment was definitely detected by MALDI-TOF measurement. A DSC test implied that the resulting polyether has excellent segment motion performance potentially beneficial for the ion transport of polymer electrolytes. Moreover, a TGA assay showed that this hyperbranched polymer possesses high thermostability as compared to its liquid counterpart. The ion conductivity was measured to reach 5.6 × 10−5 S/cm at room temperature and 6.3 × 10−4 S/cm at 80 °C after doped with LiTFSI at a ratio of Li:O = 0.05, presenting the promise to meet the practical requirement of lithium ion batteries for polymer electrolytes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3650–3665, 2006

A series of polypseudorotaxanes were synthesized from α-cyclodextrins (α-CDs) threaded onto photopolymerizable CL-PEG-CL oligomers bearing acrylate terminals. The corresponding supramolecular structured hydrogels were prepared from these polypseudorotaxanes in a mixed solvent of H 2 O and DMSO via in situ photopolymerization under UV irradiation. The structure and properties of the gels were characterized by FTIR, TGA–DTG and WAXD. The results show that α-CDs are threaded and immobilized onto the network chains of the hydrogel with crosslinking junctions as stoppers topologically, and the feed molar ratio of α-CDs to the macromers affects the hydrogel structure and the water distribution in the hydrogel. These supramolecular structured hydrogels may be good candidates for biomaterial applications.