Molecularly-imprinted material made by template-directed synthesis

• US 6,310,110 B1
• Filed: 07/30/1999
• Issued: 10/30/2001
• Est. Priority Date: 07/30/1999
• Status: Expired due to Fees

• Current Assignee: Navy The USA As Represented By The Secretary of The
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Dordick, Jonathan S., Turner, David C., Clark, Douglas S., Markowitz, Michael A., Ratna, Banahalli R., Schoen, Paul E., Gaber, Bruce P., Kust, Paul R.
• Primary Examiner(s): Nutter, Nathan M.
• Application Number:
  US09/363,819
• Time in Patent Office: 823 Days
• Field of Search: 521/99, 521/100, 521/102, 521/106, 521/107, 521/108, 521/109, 521/110, 521/111, 521/117, 521/120, 521/121, 521/128, 521/131, 521/154, 436/518, 436/524, 436/527, 436/531, 436/8, 501/12, 501/32, 501/80, 516/98, 516/99, 252/408.1, 210/656, 210/660, 210/661, 210/663
• US Class Current: 521/99
• CPC Class Codes: B01J 37/00 Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 37/02 Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
• CPC Class Codes: C01P 2004/52 highly monodisperse size distribution
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/16 Pore diameter
• CPC Class Codes: C09C 1/3081 Treatment with organo-silicon compounds
• CPC Class Codes: Y10T 436/10 Composition for standardization, calibration, simulation, stabilization, preparation or preservation; processes of use in preparation for chemical testing

Abstract

A method of making a molecularly imprinted porous structure makes use of a surfactant analog of the molecule to be imprinted that has the imprint molecule portion serving as the surfactant headgroup. The surfactant analog is allowed to self-assemble in a mixture to create at least one supramolecular structure having exposed imprint groups. The imprinted porous structure is formed by adding reactive monomers to the mixture and allowing the monomers to polymerize, with the supramolecular structure serving as a template. The resulting solid structure has a shape that is complementary to the shape of the supramolecular structure and has cavities that are the mirror image of the imprint group. Similarly, molecularly imprinted particles may be made by using the surfactant to create a water-in-oil microemulsion wherein the imprint groups are exposed to the water phase. When reactive monomers are allowed to polymerize in the water phase to form particles, the surface of the particles have cavities that are the mirror image of the imprint group.

Claims

1. A method for making a material having a molecularly imprinted surface, the method comprising the steps of

(a) providing a surfactant coupled to an imprint group,

(b) combining the surfactant with a solvent to form a mixture and maintaining the mixture so that molecules of the surfactant self-assemble to form at least one supramolecular structure having a surface and wherein the imprint groups are exposed on the surface,

(c) combining the mixture from step (b) with at least one reactive monomer so that the supramolecular structure serves as a template for the organizing of molecules of the reactive monomer along the surface of the supramolecular structure and around the exposed imprint groups,

(d) maintaining the mixture from step (c) so that the reactive monomers react with each other to form a solid structure having a surface topography complementary to the surface topography of the supramolecular structure and having indentations complementary to the shape of the exposed imprint groups, and

(e) removing the supramolecular structure from the solid structure.

2. A method for making a material having a molecularly imprinted surface, the method comprising the steps of

(a) providing a surfactant compound having a headgroup portion, wherein the headgroup portion comprises an imprint group,

(b) combining the surfactant compound, a solvent and at least one reactive monomer to form a mixture and maintaining the mixture so that molecules of the surfactant compound self-assemble to form at least one supramolecular structure having a surface wherein the imprint groups are exposed on the surface and so that the supramolecular structure serves as a template wherein the molecules of the reactive monomer self-organize along the surface of the supramolecular structure and around the exposed imprint groups,

(c) maintaining the mixture from step (b) so that the reactive monomers react with each other to form a solid structure having a surface topography complementary to the surface topography of the supramolecular structure having indentations complementary to the shape of the exposed imprint groups, and

(d) removing the supramolecular structure from the solid structure.

3. The method of claim 2 wherein the surfactant compound is a compound that is made by the steps of

providing a hydrophilic imprint compound and

acylating the hydrophilic imprint compound to create an amphiphilic surfactant compound.

4. The method of claim 2 wherein the supramolecular structure is in the form of a micelle, reverse micelle, vesicle, bicontinuous cubic phase structure, hexagonal phase structure, or tubule.

5. The method of claim 2 wherein the reactive monomer is an organic polymer precursor.

6. The method of claim 2 wherein the reactive monomer is selected from the group consisting of acrylate, methyl methacrylate, olefins, pyrrole, saccharides, silanes, styrene, isocyanates, vinyl acetate, vinyl chloride and combinations thereof.

7. The method of claim 2 wherein the reactive monomer is an inorganic oxide precursor.

8. The method of claim 2 wherein the reactive monomer is selected from the group consisting of tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, tetramethoxygermnane, tetraisoprpoxygermnane, tetraethoxygermane, tetrabutoxygermane, aluminum n-butoxide, aluminum isoproxide, titanium ethoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium methyl phenoxide, vanadium triisopropoxide oxide, vanadium tri-n-propoxide, zirconium n-butoxide, zirconium n-propoxide and combinations thereof.

9. The method of claim 2 wherein the reactive monomer is a silicon oxide precursor.

10. The method of claim 2 wherein the reactive monomer is an alkoxysilane.

11. The method of claim 2 wherein the mixture of step (b) includes a non-functionalized reactive monomer, a reactive monomer having an amine functional group, a reactive monomer having a carboxyl functional group and reactive monomer having a dihydroimidazole functional group.

12. The method of claim 2 wherein the mixture of step (b) includes a non-functionalized reactive monomer and at least one reactive monomer having a functional moiety selected from group consisting of primary amines, secondary amines, tertiary amines, quaternary amines, hydroxyl, carboxylate, sulfhydryl, amino acids, metal chelates, ureido, urea, thiourea, amidine, methyl, phenyl, fluorocarbons, nucleotides, phosphonucleotides, phosphates, saccharides and combinations thereof.

13. The method of claim 2 wherein the mixture of step (b) includes at least one additional surfactant.

14. The method of claim 2 wherein, in step (b), the surfactant and the solvent are combined first and the mixture of the surfactant and solvent is maintained so that molecules of the surfactant compound self-assemble to form at least one supramolecular structure having exposed imprint groups and wherein subsequently, the reactive monomer is added to the mixture.

15. The method of claim 2

wherein the imprint group includes at least one functional moiety,

wherein the mixture of claim (b) includes at least one reactive monomer that has a complementary functional moiety that binds reversibly to at least one functional moiety of the imprint group,

wherein, in step (c), as molecules of the reactive monomers self-organize along the surface of the supramolecular structure and around the exposed imprint groups, the molecules of the reactive monomers having complementary functional moieties become spatially distributed with respect to molecules of the imprint group so that the complementary functional moieties of the reactive monomers bind reversibly to the functional moieties of molecules of the imprint group, and

wherein, in the solid structure formed in step (d), the spatial distribution of the reactive monomers having complementary functional moieties is retained.