IP Library Granted Patent US 9,733,184
Granted Patent B2
US 9,733,184 · App. 14/389,702 · Granted Aug 15, 2017

Visual detection of mercury ions

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Quick Facts
Patent No.
US 9,733,184
App. No.
14/389,702
Granted
Aug 15, 2017
Kind
B2
Abstract

Composite materials comprising a mesoflower structure, methods of preparing the composite material, and methods of detecting heavy metal ion using the composite material are described herein. In some embodiments, a silica-coated gold mesoflower with a layer of silver quantum clusters may be capable of detecting Hg 2+ ions in a sample at zeptomolar concentrations.

Claims (66)

1. A metallic composite material comprising a mesoflower structure having a metal core and a plurality of luminescent nanoparticles affixed to the mesoflower structure, wherein:

the composite material has a first luminescent emission when heavy metal ions are not bound to the composite material;

the composite material has a second luminescent emission when the heavy metal ions are bound to the composite material, wherein the second luminescent emission is different from the first luminescent emission; and

a delta of luminescent emission between the first luminescent emission and the second luminescent emission is observable in the heavy metal ions at a concentration of about 100 femtomolar to about 0.1 zeptomolar.

2. The composite material of claim 1 , wherein the metal core comprises gold.

3. The composite material of claim 2 , wherein:

the metal core further comprises a layer of silver, nickel, cobalt, platinum, or a combination thereof.

4. The composite material of claim 1 , wherein the plurality of luminescent nanoparticles is separated from the metal core by at least one inert layer.

5. The composite material of claim 4 , wherein the at least one inert layer comprises aluminum oxide, titanium dioxide, zirconium oxide, silicon dioxide, or a combination thereof.

6. The composite material of claim 4 , wherein the at least one inert layer further comprises a fluorescent dye.

7. The composite material of claim 6 , wherein:

the fluorescent dye is selected from fluorescein isothiocyanate and derivatives of naphthalene, xanthene, pyrene, and acridine; and

the change in the luminescent emission when the heavy metal ions are bound to the composite material is a shift to a different wavelength.

8. The composite material of claim 1 , wherein the plurality of luminescent nanoparticles comprise quantum clusters of at least one of Au 25 clusters, Au 18 clusters, or Ag 15 clusters.

9. The composite material of claim 8 , wherein the quantum clusters comprise Ag 15 clusters confined in bovine serum albumin, and the composite material exhibits red luminescent emission when illuminated with light of a wavelength of about 490 nanometers and the heavy metal ions are not bound to the composite material.

10. The composite material of claim 1 , wherein:

the change in the luminescent emission has a sensitivity to the heavy metal ions at a concentration of about 0.1 zeptomolar; and

the change in the luminescent emission is a shift to a different wavelength, a diminished intensity, an intensified intensity, or a combination thereof.

11. The composite material of claim 1 , wherein:

the mesoflower structure has a dimension of about 500 nm to about 4 μm;

the heavy metal ions are selected from the group consisting of mercury, lead, nickel, arsenic, aluminum, cobalt, chromium, manganese, copper, cadmium, and combinations thereof;

the heavy metal ions selectively bound by the composite material are selectively bound relative to other heavy metal ions; and

the change in the luminescent emission when the heavy metal ions are bound to the composite material is a diminished intensity.

12. A method of preparing a metallic composite material, the method comprising:

providing a mesoflower structure having a metal core;

contacting the mesoflower structure with a solution comprising tetraethyl orthosilicate or (3-aminopropyl)trimethoxysilane to produce a solution comprising a silicon dioxide coated mesoflower structure;

isolating the silicon dioxide coated mesoflower structure;

providing a plurality of luminescent nanoparticles; and

contacting the silicon dioxide coated mesoflower structure with the plurality of luminescent nanoparticles to produce a solution comprising the composite material, wherein the composite material permits heavy metal ion detection at a concentration of about 100 femtomolar to about 0.1 zeptomolar.

13. The method of claim 12 , wherein:

the metal core comprises gold coated with a layer of silver, nickel, cobalt, platinum, or a combination thereof; and

the plurality of luminescent nanoparticles comprise quantum clusters of at least one of Au 25 clusters, Au 18 clusters, or Ag 15 clusters.

14. The method of claim 13 , wherein the composite material comprises Ag 15 clusters confined in bovine serum albumin and exhibits red luminescent emission when illuminated with light of a wavelength of about 490 nanometers.

15. The method of claim 12 , wherein the solution comprising tetraethyl orthosilicate or (3-aminopropyl)trimethoxysilane further comprises a fluorescent dye.

16. The composite material of claim 15 , wherein the fluorescent dye is selected from fluorescein isothiocyanate and derivatives of naphthalene, xanthene, pyrene, and acridine.

17. The method of claim 12 , wherein isolating the silicon dioxide coated mesoflower structure comprises:

centrifuging the solution comprising the silicon dioxide coated mesoflower structure;

decanting to produce a residue comprising the silicon dioxide coated mesoflower structure;

adding water to the residue comprising the silicon dioxide coated mesoflower structure; and

repeating the centrifuging and decanting steps one to five times to produce a residue comprising a substantially pure silicon dioxide coated mesoflower structure having a dimension that is about 500 nm to about 2 μm.

18. A method of detecting heavy metal ions in a sample, the method comprising:

providing a metallic composite material, wherein the composite material comprises a mesoflower structure having a metal core and a plurality of luminescent nanoparticles affixed to the mesoflower structure, and wherein the composite material has a first luminescent emission when the heavy metal ions are not bound to the composite material;

contacting the composite material with the sample containing, or suspected of containing, the heavy metal ions;

exposing the composite material to light comprising at least one wavelength capable of exciting the mesoflower structure to produce a second luminescent emission; and

measuring the second luminescent emission of the composite material, wherein a second luminescent emission different from the first luminescent emission following contact with the sample indicates that the heavy metal ions are bound to the composite material and that the heavy metal ions are present in the sample, wherein a delta of luminescent emission between the first luminescent emission and the second luminescent emission is observable in the heavy metal ions at a concentration of about 100 femtomolar to about 0.1 zeptomolar.

19. The method of claim 18 , wherein:

providing a composite material comprises making a solution comprising the composite material; and

contacting the composite material with the sample containing, or suspected of containing, the heavy metal ions comprises adding the sample containing, or suspected of containing, the heavy metal ions to the solution comprising the composite material.

20. The method of claim 18 , wherein:

providing the composite material comprises making a drop-cast film of the composite material; and

contacting the composite material with the sample containing, or suspected of containing, the heavy metal ions comprises adding the sample containing, or suspected of containing, the heavy metal ions to the drop-cast film of the composite material.

21. The method of claim 18 , wherein the metal core comprises gold optionally coated with a layer of silver, nickel, cobalt, platinum, or a combination thereof.

22. The method of claim 18 , wherein the plurality of luminescent nanoparticles is separated from the mesoflower structure by at least one inert metal oxide layer.

23. The composite material of claim 22 , wherein the at least one inert layer comprises aluminum oxide, titanium dioxide, zirconium oxide, silicon dioxide, or a combination thereof.

24. The method of claim 22 , wherein:

the at least one inert layer further comprises a fluorescent dye selected from fluorescein isothiocyanate and derivatives of naphthalene, xanthene, pyrene, and acridine; and

the change in the luminescent emission is a shift to a different wavelength.

25. The method of claim 18 , wherein the plurality of luminescent nanoparticles comprise quantum clusters of at least one of Au 25 clusters, Au 18 clusters, or Ag 15 clusters confined in bovine serum albumin or glutathione.

26. The method of claim 18 , wherein:

the composite material exhibits red luminescent emission when illuminated with light of a wavelength of about 490 nanometers; and

the change in the luminescent emission is a shift to a different wavelength, a diminished intensity, an intensified intensity, or a combination thereof.

27. The method of claim 18 , wherein the heavy metal ions are selected from the group consisting of mercury, lead, nickel, arsenic, aluminum, cobalt, chromium, manganese, copper, cadmium, and combinations thereof.

28. The method of claim 18 , wherein:

the heavy metal ions are mercury ions and wherein the mercury ions are selectively detected from other heavy metal ions; and

the change in the luminescent emission is a diminished intensity.

29. The method of claim 18 , wherein the method is a method for detecting the heavy metal ions at a femtomolar, attomolar, or zeptomolar concentration, and the sample containing, or suspected of containing, the heavy metal ions contains the heavy metal ions at a femtomolar, attomolar, or zeptomolar concentration, and the change in the luminescent emission of the composite material following contact with the sample has a magnitude proportional to an amount of heavy metal in the sample.

Assignments (3)
RELEASE OF SECURITY INTEREST Recorded Jul 31, 2019
From: CRESTLINE DIRECT FINANCE, L.P.
To: EMPIRE TECHNOLOGY DEVELOPMENT LLC
Reel/Frame 049924/0794 →
SECURITY INTEREST Recorded Jan 29, 2019
From: EMPIRE TECHNOLOGY DEVELOPMENT LLC
To: CRESTLINE DIRECT FINANCE, L.P.
Reel/Frame 048373/0217 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 30, 2014
From: THALAPPIL, PRADEEP; MATHEW, AMMU; SAJANLAL, PANIKKANVALAPPIL RAVINDRANATHAN
To: INDIAN INSTITUTE OF TECHNOLOGY MADRAS
Reel/Frame 033868/0443 →