Biobased Polymer Coating Using Catechol Derivative Urushiol.

We have investigated the mechanism of the superior mechanical robustness of coated thin films of the catechol derivative urushiol. We synthesized hydrogenated urushiol (h-urushiol) by hydrogenating the double bonds in the long alkyl side chain of urushiol, and the physical properties of thin films of mixtures of urushiol and h-urushiol were evaluated. Atomic force microscopy observations revealed that these coated thin films have a homogeneous surface with no phase separation, regardless of the h-urushiol content, arising from the similarity of the chemical structures. The films showed good adhesive properties because the adhesion originates from the catechol structure. In contrast, curing time depended strongly upon the h-urushiol content. The curing of the h-urushiol thin film took 12 h, whereas the urushiol thin film was cured within 10 min. Moreover, the strain-induced elastic buckling instability for mechanical measurements test and the bulge test confirmed that the increase in the h-urushiol content decreased the mechanical strength. Because the double bonds in the urushiol side chain contribute to forming the highly cross-linked structure, the lack of double bonds in h-urushiol resulted in the slow curing and low mechanical strength. Interestingly, the mechanical robustness started to increase over 80 mol % h-urushiol. The saturated long alkyl side chain of h-urushiol faced the surface, and the regular structure of the uniform side chain may improve the mechanical properties of the coated film. Our results will help to develop biomimetic catechol-based coatings.

Scaffold for growing dense polymer brushes from a versatile substrate.

We have demonstrated a universal approach to growing polymer brushes from various substrates. Urushiol was mixed with initiator-containing catechol, and it was spin-coated or cast on various substrates. Because urushiol is strongly adhered to various substrates, the thin film can serve as a general scaffold for grafting polymer brushes from various substrates. Note that the film was formed even onto the surface of polyolefins and thermosetting resins that are known as chemically inert materials to functionalize the surface. Moreover, the initiator-immobilized scaffold showed mechanical robustness and chemical inertness because of the flexible long unsaturated hydrocarbon side chain of urushiol. After the grafting of polyelectrolyte PMTAC polymer brushes, the material obtained exhibited hydrophilicity, typical of PMTAC. The concept shown here could provide a general approach for grafting practical polymer brushes from various substrates.

Light-Triggered Adhesion of Water-Soluble Polymers with a Caged Catechol Group.

An acrylamide-type copolymer containing hydroxyl, amino, and ortho-nitrobenzyl protected catechol groups was synthesized as a functional mussel adhesive protein (MAP) mimetic. The resulting copolymer was stable even in the oxidative condition. Light irradiation to aqueous solution of the copolymer induced deprotection of a caged compound to give a native catechol group and triggered an oxidative cross-linking reaction to afford the adhesive gel. Two glass plates were adhered through light-activated gelation of the polymer solution in a humid air atmosphere. A novel type of light-activated adhesive with excellent stability and light controllable activation properties was successfully fabricated by modification of the MAP mimetic copolymer.

Competition between Oxidation and Coordination in Cross-Linking of Polystyrene Copolymer Containing Catechol Groups.

In gelation chemistry, catechol groups are used as cross-linking points. Both oxidation and coordination effects of catechol were investigated for their unique features in chemistry by spectroscopic measurements. Polystyrene copolymers containing catechol groups were synthesized by free radical copolymerization of styrene and N-2-(3',4'-ditriethylsilyloxyphenyl)ethyl methacrylamide, and the successive deprotection reaction was catalyzed by tetra-n-butylammonium fluoride. The copolymer containing catechol units afforded a dual cross-linking system based on completely different coordination and oxidation chemistries, and the competing cross-linking mechanisms are discussed. These findings are useful and important for paving the way for designing a novel bioinspired artificial adhesive surface coating and curing system.

Convenient modular method for affinity labeling (MoAL method) based on a catalytic amidation.

A modular methodology for affinity labeling, in which three essential elements generally constituting affinity probes are prepared separately as individual molecules, has been developed based on a catalytic amidation.

Spontaneous membrane fusion induced by chemical formation of ceramides in a lipid bilayer.

Mere chemical generation of ceramide and related double-chain lipids in the membrane of small unilamellar vesicles (SUVs) induces fusion of the vesicles. The lipids can be successfully prepared by dehydrocondensation between single-chain lipids (fatty acids and sphingosine or its analogues) in a lipid bilayer of the SUV by using a combination of 2-chloro-4,6-dimethoxy-1,3,5-triazine and amphiphilic tertiary amine catalysts, a process that can be compared to a successive enzyme model system for a fatty acyl-CoA synthetase followed by acyltransferase. The SUV spontaneously undergoes membrane fusion upon this internal chemical stimulation by the artificial enzyme system.

Mixing behavior of fluorinated and hydrogenated gemini surfactants at the air-water interface.

Mixing behavior of hydrogenated and fluorinated cationic gemini surfactants was studied at the air-water interface by Brewster angle microscopy and pi-A isotherm curves. In the bulk, these two molecules did not mix and showed phase separation. At the air-water interface, if a monolayer was formed by separate deposition of the two solutions, they formed separate domains, and the compression occurred in two steps: first the domains with hydrogenated gemini surfactant were compressed until they showed collapse; then the domains with fluorinated gemini surfactant were compressed. If the two solutions were mixed before the deposition, they remained mixed upon compression; on the other hand, separate domains under separate deposition were shown to mix if the subphase was heated.

Design of novel biointerfaces (II). Fabrication of self-organized porous polymer film with highly uniform pores.

Application of porous polymer materials to novel bio-interfaces for tissue engineering scaffold and artificial organs including blood filters, dialyzer, and oxygenator membranes have been in progress. The present study describes the fabrication and characterization of self-organized highly regular porous polymer films with uniform pore sizes are prepared by simple casting technique. Various fabrication parameters affecting the pore size such as polymer concentration, boiling point of solvent, cast volume and substrate are studied. The pore size can be controlled in the range from 1 to 50 microm by changing the evaporation rate of the polymer solutions. The porous film with uniform pore size is used for tissue engineering scaffold and cell separation membrane. To simulate the leukocyte eliminating from human blood, the porous film was attached to a module. The films with 5-9 microm pores provided the complete selectivity of separation for the leukocyte from the whole blood. The leukocyte elimination ratio depends on pore structures (size and depth) as well as recovery of platelet and erythrocyte.