Fibrous crystalline hydrogels formed from polymers possessing a linear poly(ethyleneimine) backbone.
Novel thermoreversible physical hydrogels formed from polymers with linear and star architectures possessing a linear poly(ethyleneimine) (PEI) backbone have been investigated. The hydrogelation occurred simply upon natural cooling of hot aqueous solutions of PEIs to room temperature. The X-ray diffraction and differential scanning calorimetry measurements for the resultant hydrogels unambiguously indicated that the hydrogelation originated from the formation of dihydrate crystalline structures of PEI. These crystalline hydrogels are structurally unique and hierarchical. Microscopic images revealed that the morphologies of the crystalline hydrogels depend on their molecular architectures. The linear PEI resulted in branched fibrous bundles organized by unit crystalline nanofibers with a width of ca. 5-7 nm. The six-armed star with benzene ring core produced fanlike fibrous bundles while the four-armed star with porphyrin core assembled into asterlike aggregates. The critical concentration of gelation (C(G)) was low (about 0.2 approximately 0.3%) and the thermoreversible gel-sol transition temperatures (T(G)) were controllable from approximately 43 to approximately 79 degrees C. The hydrogels formed in the presence of the various aqueous additives including organic solvents, hydrophilic polymers, physical cross-linker, chemical cross-linker, and base enabling modification and functionalization during synthesis. The mechanical properties of the hydrogels could be improved by chemical cross-linking of preformed hydrogels by glutaraldehyde. Physically and physical/chemical cross-linked hydrogels served as excellent template roles in biomimetic silicification, which produced silica-PEI hybrid powder or monolith constructed by nanofibers.
Yuan
Jian-Jun
JJ
Synthetic Chemistry Laboratory, Kawamura Institute of Chemical Research, 631 Sakado, Sakura, Chiba 285-0078, Japan.
Jin
Ren-Hua
RH
D000641:Ammonia; D002152:Calorimetry, Differential Scanning; D020100:Hydrogels / Q000737:chemistry*; D008855:Microscopy, Electron, Scanning; D046529:Microscopy, Electron, Transmission; D015394:Molecular Structure; D044367:Phase Transition; D011094:Polyethyleneimine / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry; D012997:Solvents; D013696:Temperature; D014961:X-Ray Diffraction
D020100:Hydrogels; D012997:Solvents; D012822:Silicon Dioxide; D000641:Ammonia; D011094:Polyethyleneimine