Molecularly imprinted polymer solution anion sensor

• US 6,749,811 B2
• Filed: 10/16/2002
• Issued: 06/15/2004
• Est. Priority Date: 04/28/1998
• Status: Active Grant

• Current Assignee: Johns Hopkins University
• Original Assignee: Johns Hopkins University
• Inventors: Murray, George M.
• Primary Examiner(s): Warden, Jill
• Assistant Examiner(s): SINES, BRIAN J
• Application Number:
  US10/272,834
• Publication Number:
  US 20030129092A1
• Time in Patent Office: 608 Days
• Field of Search: 422/91, 422/88, 422/82.05, 422/82.07, 422/82.08, 422/50, 422/52, 422/55, 422/68.1, 422/83, 436/43, 436/164, 436/166, 436/172, 73/10.1, 73/10.2, 73/232, 73/530.1
• US Class Current: 422/91
• CPC Class Codes: B01J 20/268 Polymers created by use of a template, e.g. molecularly imprinted polymers
• CPC Class Codes: G01N 2021/772 Tip coated light guide
• CPC Class Codes: G01N 21/648 using evanescent coupling or surface plasmon coupling for the excitation of fluorescence
• CPC Class Codes: G01N 21/7703 using reagent-clad optical fibres or optical waveguides using measurement of total internal reflection or attenuated total reflection G01N21/552; optical fibres or waveguides per se G02B
• CPC Class Codes: G01N 2600/00 Assays involving molecular imprinted polymers/polymers created around a molecular template
• CPC Class Codes: G01N 33/84 involving inorganic compounds or pH
• CPC Class Codes: Y10T 436/11 Automated chemical analysis

Abstract

Devices for measuring and detecting a wide variety of analytes, including polyatomic anions, such as organophosphorus pesticides and nerve agents are provided. The devices function by selectively binding an analyte to a luminescent functionality-imprinted copolymer. The copolymers possess a securely bound luminescent lanthanide ion, such as Eu3+, in a coordination complex that has been imprinted to bind the chemical functionality. Also provided are methods for producing the lanthanide-containing molecularly imprinted polymers of the invention.

Claims

1. A sensor device for detecting an analyte comprising a molecularly imprinted polymer containing a chelated lanthanide, said chelated lanthanide comprising a lanthanide ion wherein said lanthanide ion is a europium or terbium ion, wherein the lanthanide ion is chelated with the polymerized derivate(s) of one or more ligands selected from the group consisting of vinyldibenzoylmethane, divinyldibenzoylmethane, vinyl-substituted 1,10-phenanthroline, and mixtures of two or more thereof, said chelated lanthanide capable of binding the analyte to be detected and having operatively associated therewith:

a light source for generating excitation energy for said chelated lanthanide; and

a detector for detecting luminescent energy generated by said chelated lanthanide upon excitation.

2. The sensor device of claim 1 wherein the light source is selected from the group consisting of an argon laser, blue laser, tunable laser, light emitting diode, and combinations of two or more thereof.

3. The sensor device of claim 2 wherein the light source is a light emitting diode.

4. The sensor device of claim 1 wherein the detector is selected from the group consisting of a spectrophotometer, spectrometer, photomultiplier tube, monochromator equipped with a CCD camera, filters, the naked eye, and combinations of two or more thereof.

5. The sensor device of claim 1 further comprising at least one optical fiber, having a proximal end and a distal end, for transmitting light energy, wherein said molecularly imprinted polymer is disposed onto distal end of the optical fiber, said light source is operatively associated with said optical fiber such that said fiber is capable of transmitting excitation energy generated by the light source to said molecularly imprinted polymer, and said detector is operatively associated with said optical fiber such that said detector is capable of detecting luminescence from said chelated lanthanide.

9. A method for detecting a target analyte comprising providing a solution comprising an analyte to be detected and contacting said solution with the molecularly imprinted polymer of a sensor device of claims 1 or 6.

10. The method of claim 9 wherein said analyte is bound to a chelated lanthanide in said molecularly imprinted polymer.

11. The method of claim 10 wherein at least a portion of said molecularly imprinted polymer of said device is immersed within said solution.

6. A sensor device for detecting an analyte comprising a molecularly imprinted polymer containing a chelated lanthanide, said chelated lanthanide comprising a lanthanide ion wherein said lanthanide ion is a +3 europium ion, wherein the lanthanide ion is chelated with the polymerized derivate(s) of one or more ligands selected from the group consisting of vinyldibenzoylmethane, divinyldibenzoylmethane, vinyl-substituted 1,10-phenanthroline, and mixtures of two or more thereof, said chelated lanthanide capable of binding the analyte to be detected and having operatively associated therewith:

a light source for generating excitation energy for said chelated lanthanide;

a detector for detecting luminescent energy generated by said chelated lanthanide upon excitation; and

at least one optical fiber, having a proximal end and a distal end, for transmitting light energy, wherein said molecularly imprinted polymer is disposed on the distal end of the optical fiber, said light source is operatively associated with said optical fiber such that said fiber is capable of transmitting excitation energy generated by the light source to said molecularly imprinted polymer, and said detector is operatively associated with said optical fiber such that said detector is capable of detecting luminescence from said chelated lanthanide.

7. The sensor device of claim 6 wherein the light source is a light emitting diode.

8. The sensor device of claim 7 wherein the detector is selected from the group consisting of a spectrophotometer, spectrometer, photomultiplier tube, monochromator equipped with a CCD camera, filters, the naked eye, and combinations of two or more thereof.

12. A method of making a molecularly imprinted polymer comprising:

mixing a lanthanide salt with one or more polymerizable lanthanide-coordinating ligand compounds and a polyatomic anion target analyte imprint molecule under conditions effective to produce a chelated lanthanide-analyte complex;

co-polymerizing the lanthanide-analyte complex with one or more cross-linking monomers, and one or more matrix monomers to form a polymer structure; and

removing the imprint molecule from the polymer structure to form an MIP.

13. The method of claim 12 wherein said lanthanide salt is a salt of a lanthanide selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

14. The method of claim 13 wherein said polymerizable ligand compounds are selected from the group consisting of 4-vinyl benzoic acid, methyl-3,5-divinyl benzoate, 4-vinyl-2-hydroxybenzaldehyde oxime, 2-hydroxy-1,2-di-4-vinylphenylethanone (benzoin oxime vinyl derivative), vinyldibenzoylmethane, divinyldibenzoylmethane, vinyl-substituted 1,10-phenanthroline, and mixtures of two or more thereof.

15. The method of claim 14 wherein said polyatomic anion is selected from the group consisting of nitrate, perchlorate, and phosphates.

16. The method of claim 12 wherein said matrix monomer is selected from the group consisting of divinyl benzene, styrene, and azobisisobutylnitrile.