Mechanically interlocked molecules-based materials for 3-D printing

A method of manufacturing a supramolecular polypseudorotaxane hydrogel composition capable of reversible 3-D structural deformation, said method comprising:

• mixing a solvent, an at least partially linear co-polymer, and a plurality of macrocyclic rings,
• wherein the at least partially linear co-polymer comprises groups capable of covalent crosslinking between the at least partially linear co-polymers,
• wherein the groups capable of covalent crosslinking between the at least partially linear co-polymers comprise N-aminoethyl-methylacrylamide,
• wherein the macrocyclic rings comprise first macrocyclic rings that form a pseudorotaxane in the composition, and second macrocyclic rings that do not form a pseudorotaxane in the composition, and
• wherein the hydrogel composition has a viscosity which allows for 3-D printing of the hydrogel to form a 3-D structure, and an elastic modulus after crosslinking that allows for the 3-D structure to undergo reversible 3-D structural deformation upon change of solvent conditions.

A method of manufacturing a supramolecular polypseudorotaxane hydrogel composition capable of reversible 3-D structural deformation, said method comprising:

• mixing a solvent, an at least partially linear co-polymer, and a plurality of macrocyclic rings,
• wherein the at least partially linear co-polymer comprises groups capable of covalent crosslinking between the at least partially linear co-polymers,
• wherein the macrocyclic rings comprise first macrocyclic rings that form a pseudorotaxane in the composition, and second macrocyclic rings that do not form a pseudorotaxane in the composition,
• wherein the first macrocyclic rings are present in an amount of from about 20 to about 35% w/v of the composition, and
• wherein the hydrogel composition has a viscosity which allows for 3-D printing of the hydrogel to form a 3-D structure, and an elastic modulus after crosslinking that allows for the 3-D structure to undergo reversible 3-D structural deformation upon change of solvent conditions.

A method of manufacturing a supramolecular polypseudorotaxane hydrogel composition capable of reversible 3-D structural deformation, said method comprising:

• mixing a solvent, an at least partially linear co-polymer, and a plurality of macrocyclic rings,
• wherein the at least partially linear co-polymer comprises groups capable of covalent crosslinking between the at least partially linear co-polymers,
• wherein the molar ratio of the at least partially linear co-polymer to the macrocyclic rings is about 30:1 to about 60:1,
• wherein the macrocyclic rings comprise first macrocyclic rings that form a pseudorotaxane in the composition, and second macrocyclic rings that do not form a pseudorotaxane in the composition, and
• wherein the hydrogel composition has a viscosity which allows for 3-D printing of the hydrogel to form a 3-D structure, and an elastic modulus after crosslinking that allows for the 3-D structure to undergo reversible 3-D structural deformation upon change of solvent conditions.

A method of manufacturing a supramolecular polypseudorotaxane hydrogel composition capable of reversible 3-D structural deformation, said method comprising:

• mixing a solvent, an at least partially linear co-polymer, and a plurality of macrocyclic rings,
• wherein the at least partially linear co-polymer comprises groups capable of covalent crosslinking between the at least partially linear co-polymers,
• wherein the molar ratio of the at least partially linear co-polymer to the macrocyclic rings is about 35:1 to about 55:1,
• wherein the macrocyclic rings comprise first macrocyclic rings that form a pseudorotaxane in the composition, and second macrocyclic rings that do not form a pseudorotaxane in the composition, and
• wherein the hydrogel composition has a viscosity which allows for 3-D printing of the hydrogel to form a 3-D structure, and an elastic modulus after crosslinking that allows for the 3-D structure to undergo reversible 3-D structural deformation upon change of solvent conditions.

A method of manufacturing a supramolecular polypseudorotaxane hydrogel composition capable of reversible 3-D structural deformation, said method comprising:

• mixing a solvent, an at least partially linear co-polymer, and a plurality of macrocyclic rings,
• wherein the at least partially linear co-polymer comprises groups capable of covalent crosslinking between the at least partially linear co-polymers,
• wherein the macrocyclic rings comprise first macrocyclic rings that form a pseudorotaxane in the composition, and second macrocyclic rings that do not form a pseudorotaxane in the composition, and
• wherein the hydrogel composition has a viscosity which allows for 3-D printing of the hydrogel to form a 3-D structure, and an elastic modulus after crosslinking that allows for the 3-D structure to undergo reversible 3-D structural deformation upon change of solvent conditions, and
• wherein the formed hydrogel composition further comprises a plurality of hexagonal crystalline domains, wherein the hexagonal crystalline domains comprise non-covalent interactions between the plurality of first macrocyclic rings and second macrocyclic rings, and wherein the hexagonal crystalline domains are capable of rapidly and reversibly deforming and reforming after application and removal of an external mechanical force.

A method of manufacturing a supramolecular polypseudorotaxane hydrogel composition capable of reversible 3-D structural deformation, said method comprising:

• mixing a solvent, an at least partially linear co-polymer, and a plurality of macrocyclic rings,
• wherein the at least partially linear co-polymer comprises groups capable of covalent crosslinking between the at least partially linear co-polymers,
• wherein the macrocyclic rings comprise first macrocyclic rings that form a pseudorotaxane in the composition, and second macrocyclic rings that do not form a pseudorotaxane in the composition, and
• wherein the hydrogel composition has a viscosity which allows for 3-D printing of the hydrogel to form a 3-D structure, and an elastic modulus after crosslinking that allows for the 3-D structure to undergo reversible 3-D structural deformation upon change of solvent conditions, and
• wherein the viscosity of the hydrogel composition at a shear rate of 1 s−1 and 25° C. is between 1 and 500 Pa·s.