Synthesis, uses and compositions of crystal hydrogels

• US 7,347,988 B2
• Filed: 11/15/2002
• Issued: 03/25/2008
• Est. Priority Date: 11/15/2001
• Status: Expired due to Fees

• Current Assignee: University of North Texas
• Original Assignee: University of North Texas
• Inventors: Lu, Xihua, Gao, Jun, Huang, Gang, Zhou, Bo, Hu, Zhibing, Cai, Tong
• Primary Examiner(s): Wu; David W.
• Assistant Examiner(s): Hu; Henry S.
• Application Number:
  US10/295,484
• Publication Number:
  US 20040018160A1
• Time in Patent Office: 1,957 Days
• Field of Search: 424/63, 424/486, 424/488, 525/88, 524/563
• US Class Current: 424/63
• CPC Class Codes: C08F 220/56 Acrylamide; Methacrylamide
• CPC Class Codes: C08J 3/075 Macromolecular gels
• CPC Class Codes: G01N 2021/7723 Swelling part, also for adsorption sensor, i.e. without chemical reaction
• CPC Class Codes: G02B 1/04 made of organic materials, e.g. plastics G02B1/08 takes precedence

Abstract

A method is disclosed for creating hydrogels with ordered crystalline structures that exhibit a characteristic colored opalescence. In addition to the unique optical properties, these materials contain a large amount of water in their crosslinked networks. The manufacturing processes include synthesizing monodispersed hydrogel nanoparticles containing specific reactive functional groups, self-assembly of these particles to form a crystalline structure, and subsequent crosslinking neighboring spheres to stabilize the entire network. Polymerizing a hydrogel monomeric composition around the crystalline structure can enhance the mechanical strength. The resulting network is dimensionally and thermodynamically stabile under various pH and temperature conditions. The color and volume of these crystalline hydrogel networks can reversibly change in response to external stimuli such as temperature, pH and other environmental conditions. These new materials may lead to a variety of technological and artistic applications, ranging from sensors, displays, controlled drug delivery devices, jewelry and decorative consumer products.

Claims

1. A crystal hydrogel material comprising covalently bonded, periodically stacked, monodispersed gel nanoparticles dispersed throughout a liquid medium in a crystalline lattice, wherein neighboring gel nanoparticles are covalently linked using small molecular crosslinkers, and wherein the crystal hydrogel material demonstrates visible opalescence contributed by Bragg diffraction from the crystalline lattice of periodically stacked nanoparticles.

2. The crystal hydrogel material of claim 1 where the medium is water.

3. The crystal hydrogel material of claim 1, wherein covalent bonding contributes to mechanical, dimensional, and thermal stability of nanosphere assemblies, while periodic structure of the gel nanoparticles diffracts light to cause a range of opalescence.

4. The crystal hydrogel material of claim 1 defined further as displaying an iridescent color with good transparency and no sedimentation in the absence of an index-matching or a density-matching fluid.

5. The crystal hydrogel material of claim 1 defined further as containing at least 75% water by weight.

6. The crystal hydrogel material of claim 1 defined further as containing about 90% water by weight.

7. The crystal hydrogel material of claim 1 defined further as containing at least 97% water by weight.

8. The crystal hydrogel material of claim 1 defined further as changing in color and volume in response to environmental conditions.

9. The material of claim 8 where the environmental conditions are pH, temperature, electric current, ionic strength or type of solvent.

10. The crystal hydrogel material of claim 1 defined further as exhibiting different colors when different particle sizes, particle concentrations, chemical composition of the particles or reaction temperatures are used to produce the particles.

11. The crystal hydrogel material of claim 1 in which crystalline grain size changes as a function of particle size, particle concentration, particle stacking or particle chemical composition.

12. The crystal hydrogel material of claim 1 where optimum conditions in which to form said crystal hydrogel are dependent upon specific temperature and pH ranges.

13. The crystal hydrogel material of claim 1 comprising gel nanoparticles contain N-isopropylacrylamide and derivatives thereof.

14. The crystal hydrogel material of claim 1 comprising nanoparticles in a particle size range of 1-1000 nanometers in diameter.

15. The crystal hydrogel material of claim 1 comprising nanoparticles in particle size range of 1-500 nanometers diameter.

16. The crystal hydrogel material of claim 1 comprising nanoparticles in a particle size range of 20-5 00 nanometers in diameter.

17. The crystal hydrogel material of claim 1 comprising nanoparticles that are internally crosslinked using crosslinking compounds.

18. The crystal hydrogel material of claim 1 whose particles are bonded through functional groups on the surfaces of neighboring particles using crosslinking compounds.

19. The crystal hydrogel material of claim 1 comprising covalent linkages between nanoparticles that provide a thermal and dimensional stable crystal structure.

20. The crystal hydrogel material of claim 17 wherein the crosslinking compounds comprise methylene-bis-acrylamide.

21. The crystal hydrogel material of claim 18 wherein the crosslinking compounds are selected from the group consisting of divinylsulfone related analogs, glutaric dialdehyde or related analogs, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC), adipic acid dihydrazide and other related analogs.

22. The crystal hydrogel material of claim 1 encased within a secondary polymer matrix.

23. The crystal hydrogel material of claim 22 where the secondary polymer matrix are selected from the group consisting of N-isopropylacrylamide, hydroxypropylcellulose, polyvinyl alcohol, polypropylene oxide, polyethylene oxide, polyethylene oxide/polypropylene oxide copolymers, and another known hydrogel polymer.

24. The crystal hydrogel material of claim 1 or 22 whose volume and color change reversibly in response to an external stimulus.

25. The crystal hydrogel material of claim 24 where the stimulus is pH, electric field, ionic strength or temperature.

26. The crystal hydrogel material of claims 1 or 22 that, when viewed at different angles and under various lighting conditions, exhibits multiple prism-like light diffraction patterns.

27. The crystal hydrogel material of claim 1 or 22 whose optical properties change reversibly as either pH, temperature, ionic strength or electric current of the surrounding environment changes.