# US 10,119,953 B1 · Metal chalcogenide quantum dots for the detection of nitroaromatic chemicals

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- Number: US 10,119,953 B1
- Document ID: US10119953B1
- Status: Granted
- Kind: B1
- Application number: 15/705,731
- Filed: 2017-09-15
- Granted: 2018-11-06
- Earliest claimed: 2015-03-20
- Assignees: The United States of America as represented by the Secretary of the Navy
- Applicants: The United States of America, as Represented by the Secretary of the Navy
- Inventors: Alfred J. Baca; Heather A. Meylemans; Lee R. Cambrea; Lawrence Baldwin
- Web page: https://patentgrep.com/patent/US10119953B1

## CPC

- G01N 33/227: {Explosives, e.g. combustive properties thereof}
- C01G 15/006: {Compounds containing gallium, indium or thallium, with or without oxygen or hydrogen, and containing two or more other elements}
- C06B 25/04: the nitrated compound being an aromatic
- C06B 25/34: the compound being a nitrated acyclic, alicyclic or heterocyclic amine
- G01N 21/4738: {Diffuse reflection (precedence is given to G01N21/55 - G01N21/57 if specular component is taken into consideration), e.g. also for testing fluids, fibrous materials}
- G01N 21/6428: {Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" (in vivo A61B5/00; immunoassay G01N33/53)}
- B82Y 20/00: Nanooptics, e.g. quantum optics or photonic crystals
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C01P 2002/84: by UV- or VIS- data
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- G01N 21/643: {non-biological material}
- G01N 31/22: using chemical indicators (G01N31/02 takes precedence)
- G01N 2021/4766: {Sample containing fluorescent brighteners}
- G01N 2021/6432: {Quenching}
- G01N 2021/7786: {Fluorescence}
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C06B: EXPLOSIVES OR THERMIC COMPOSITIONS (blasting F42D); MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES (compounds in general C01, C07 or C08; {demolition agents based on cementitious or like materials C04B41/0009})
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

The synthesis of AgInS2 based quantum dots and their use as fluorometric probes for the selective detection of nitroaromatic explosive chemicals, without the use of ligands specific to nitroaromatic explosive chemicals. These quantum dots allow the detection of nitroaromatic explosive molecules by eye. The present invention also represents a simple patterning method for quantum dots on substrates, including low cost filter paper. The ease of fabrication, use of less toxic materials, and the selectivity to nitroaromatic explosive chemicals results in a practical solution to the development of a portable fluorescent probe based on quantum dots for the detection of nitroaromatic explosive chemicals.

## Claims

### Claim 1

An analytical energetic material detection element, comprising: a substrate; and, one or more pluralities of functionalized fluorescent nanoparticles deposited on the substrate so that the nanoparticles are exposed to an outer environment of the detection element, wherein said nanoparticles undergo a fluorescence change in the presence of an energetic material;
each of said one or more pluralities of functionalized fluorescent nanoparticles consisting of a single selected molar ratio of at least three elemental components wherein two of the at least three elemental components are S and In, and wherein other at least three elemental components are selected from the group consisting of:
Zn, Ag, Cu, and combinations thereof wherein said one or more pluralities of functionalized fluorescent nanoparticles consisting of said single selected molar ratio of said at least three elemental components are functionalized with a ligand.

### Claim 2 (depends on 1)

The detection element of claim 1 wherein the one or more pluralities of functionalized fluorescent nanoparticles consist of a selected molar ratio of Ag, In, and S, wherein said Ag, In, and S are each present in an amount greater than zero.

### Claim 3 (depends on 1)

The detection element of claim 1 wherein the substrate comprises filter paper, cotton pad, fibrous cotton, cotton swab, cloth, litmus paper, silicon wafer, glass slide, plastic or a combination thereof.

### Claim 4 (depends on 1)

The detection element of claim 1 wherein the energetic material to be detected comprises nitroaromatics, nitramines, or combinations thereof.

### Claim 5 (depends on 1)

The detection element of claim 1 wherein the energetic material to be detected comprises octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), hexanitrohexaazaisowurtzitane (HNIW), 1,3,5-trinitrobenzene (1,3,5-TNB), 1,3-dinitrobenzene (1,3-DNB), methyl-2,4,6-trinitrophenylnitramine (Tetryl), nitrobenzene (NB), 2,4,6-trinitrotoluene (2,4,6-TNT), 4-amino-2,6-dinitrotoluene (4-Am-DNT), 2-amino-4,6-dinitrotoluene (2-Am-DNT), 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 2-nitrotoluene (2-NT), 3-Nitrotoluene (3-NT), 4-nitrotoluene (4-NT), or mixtures thereof.

### Claim 6 (depends on 1)

The detection element of claim 1 wherein each of the one or more pluralities of functionalized fluorescent nanoparticles detects a different energetic material.

### Claim 7 (depends on 1)

The detection element of claim 1 wherein the one or more pluralities of functionalized fluorescent nanoparticles are functionalized with a ligand that binds to the energetic material and facilitates a charge transfer between the energetic material and the nanoparticles.

### Claim 8 (depends on 1)

The detection element of claim 1 wherein the one or more pluralities of functionalized fluorescent nanoparticles are deposited on the substrate in a patterned configuration.

### Claim 9 (depends on 1)

The detection element of claim 1 wherein the one or more pluralities of functionalized fluorescent nanoparticles are deposited on the substrate using a photolithographic process.

### Claim 10

An assay method for detecting the presence of one or more target energetic materials in a sample, comprising:
exposing a detection element to a sample to be tested, wherein the detection element comprises a substrate and one or more pluralities of functionalized fluorescent nanoparticles deposited on the substrate so that the nanoparticles are exposed to an outer environment, wherein said nanoparticles undergo a change in fluorescence in the presence of the one or more target energetic materials;
illuminating the detection element with a source of UV light; and,
determining any change in fluorescence of the illuminated detection element to determine if it corresponds to one or more fluorescence values that is indicative of the presence of one or more of the one or more target energetic materials;
wherein said detection element comprises one or more pluralities of functionalized fluorescent nanoparticles consisting of a single selected molar ratio of at least three elemental components wherein two of the at least three elemental components are S and In, and wherein other at least three elemental components are selected from the group consisting of:
Zn, Ag, Cu, and combinations thereof wherein said one or more pluralities of functionalized fluorescent nanoparticles consisting of said single selected molar ratio of said at least three elemental components are functionalized with a ligand.

### Claim 11 (depends on 10)

The assay method of claim 10 wherein the sample to be tested is a solution and the detection element is inserted into the solution.

### Claim 12 (depends on 10)

The assay method of claim 10 wherein the one or more fluorescence values are a quenching of fluorescence, an increase in fluorescence, or a change in wavelength of fluorescence.

### Claim 13 (depends on 10)

The assay method of claim 10 wherein the one or more pluralities of functionalized fluorescent nanoparticles consisting of a selected molar ratio of Ag, In, and S,
wherein said Ag, In, and S are each present in an amount greater than zero, and
wherein said nanoparticles undergo a fluorescence change in the presence of the one or more target energetic materials.

### Claim 14 (depends on 10)

The assay method of claim 10 wherein the substrate comprises filter paper, cotton pad, fibrous cotton, cotton swab, cloth, litmus paper, silicon wafer, glass slide, or plastic.

### Claim 15 (depends on 10)

The assay method of claim 10 wherein the one or more target energetic materials to be detected comprises octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), hexanitrohexaazaisowurtzitane (HNIW), 1,3,5-trinitrobenzene (1,3,5-TNB), 1,3-dinitrobenzene (1,3-DNB), methyl-2,4,6-trinitrophenylnitramine (Tetryl), nitrobenzene (NB), 2,4,6-trinitrotoluene (2,4,6-TNT), 4-amino-2,6-dinitrotoluene (4-Am-DNT), 2-amino-4,6-dinitrotoluene (2-Am-DNT), 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 2-nitrotoluene (2-NT), 3-Nitrotoluene (3-NT), 4-nitrotoluene (4-NT), and mixtures thereof.

### Claim 16 (depends on 10)

The assay method of claim 10 wherein the plurality of functionalized fluorescent nanoparticles are functionalized with a ligand that binds to the one or more target energetic materials and facilitates a charge transfer between the one or more target energetic materials and the nanoparticles.

### Claim 17

A chemical-analysis device for detecting at least one energetic material in a sample, wherein the device comprises: at least one test element for detecting the at least one energetic material, the test element comprising a substrate having a fluorescent surface, wherein the fluorescent surface comprises at least one detection reagent which is set up to carry out at least one visually detectable reaction that results in a change in fluorescence of the at least one detection reagent in the presence of the at least one energetic material;
wherein said at least one detection reagent comprises one or more pluralities of functionalized fluorescent nanoparticles consisting of a single selected molar ratio of at least three elemental components wherein two of the at least three elemental components are S and In, and wherein other at least three elemental components are selected from the group consisting of:
Zn, Ag, Cu, and combinations thereof wherein said one or more pluralities of functionalized fluorescent nanoparticles consisting of said single selected molar ratio of said at least three elemental components are functionalized with a ligand.

### Claim 18 (depends on 17)

The chemical-analysis device of claim 17 wherein the change in the fluorescence of the at least one detection reagent is a quenching of fluorescence, an increase in fluorescence, or a change in wavelength of the fluorescence.

### Claim 19 (depends on 17)

The chemical-analysis device of claim 17 wherein the at least one test element is set up such that a stationary state of the detectable reaction is reached within a period of up to 5 seconds from exposure to the at least one energetic material.

### Claim 20 (depends on 17)

The chemical-analysis device of claim 17 wherein the at least one detection reagent comprises a plurality of functionalized fluorescent nanoparticles consisting of a selected molar ratio of Ag, In, and S,
wherein said Ag, In, and S are each present in an amount greater than zero, and
wherein said nanoparticles undergo a fluorescence change in the presence of the at least one energetic material.

### Claim 21 (depends on 20)

The chemical-analysis device of claim 20 wherein the plurality of functionalized fluorescent nanoparticles are functionalized with a ligand that binds to the at least one energetic material and facilitates a charge transfer between the at least one energetic material and the nanoparticles.

### Claim 22 (depends on 17)

The chemical-analysis device of claim 17 further comprising a source of UV light.
