Method of making nanoparticle colloid and nanoporous layer

• US 10,687,746 B2
• Filed: 08/07/2018
• Issued: 06/23/2020
• Est. Priority Date: 11/21/2017
• Status: Active Grant

• Current Assignee: UXN Co., Ltd.
• Original Assignee: UXN Co., Ltd.
• Inventors: Boo, Hankil, Chang, Rae Kyu
• Primary Examiner(s): Penny, Tabatha L
• Application Number:
  US16/057,621
• Publication Number:
  US 20190153237A1
• Time in Patent Office: 686 Days
• Field of Search: 4273761
• CPC Class Codes: A61B 2560/0475 Special features of memory means, e.g. removable memory cards
• CPC Class Codes: A61B 2562/0285 Nanoscale sensors
• CPC Class Codes: A61B 2562/125 characterised by the manufacture of electrodes
• CPC Class Codes: A61B 5/0031 Implanted circuitry
• CPC Class Codes: A61B 5/14532 for measuring glucose, e.g. by tissue impedance measurement
• CPC Class Codes: A61B 5/1473 invasive, e.g. introduced into the body by a catheter A61B5/1482 takes precedence
• CPC Class Codes: A61B 5/1486 using enzyme electrodes, e.g. with immobilised oxidase
• CPC Class Codes: A61B 5/14865 invasive, e.g. introduced into the body by a catheter or needle or using implanted sensors
• CPC Class Codes: A61B 5/72 Signal processing specially adapted for physiological signals or for diagnostic purposes character recognition, recognising digital ink, document-oriented image-based pattern recognition G06V30/00; recognition or understanding of postal images G06V30/424
• CPC Class Codes: A61B 5/742 using visual displays A61B5/339 takes precedence
• CPC Class Codes: B01J 13/0013 from a precipitate
• CPC Class Codes: B05D 5/00 Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
• CPC Class Codes: B05D 5/02 to obtain a matt or rough surface
• CPC Class Codes: B82Y 15/00 Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C09D 5/028 Pigments; Filters
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: C09D 7/67 Particle size smaller than 100 nm
• CPC Class Codes: C12Q 1/006 for glucose
• CPC Class Codes: G01N 2400/00 : Assays, e.g. immunoassays or enzyme assays, involving carbohydrates
• CPC Class Codes: G01N 27/327 : Biochemical electrodes , e.g. electrical or mechanical details for in vitro measurements
• CPC Class Codes: G01N 27/3271 : Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood amperometry per se G01N27/49; aspects concerning the enzyme reagent C12Q1/001
• CPC Class Codes: G01N 27/3335 : the membrane containing at least one organic component G01N27/3271 takes precedence; aspects concerning the enzyme reagent in enzyme electrodes C12Q1/001
• CPC Class Codes: G01N 27/4168 : Oxidation-reduction potential, e.g. for chlorination of water water analysis G01N33/18
• CPC Class Codes: G01N 33/49 : Blood chemical methods for determining blood cell populations G01N33/5094; chemical analysis of blood groups or blood types G01N33/80
• CPC Class Codes: G01N 33/66 : involving blood sugars, e.g. galactose
• CPC Class Codes: Y10S 977/773 : Nanoparticle, i.e. structure having three dimensions of 100 nm or less
• CPC Class Codes: Y10S 977/81 : Of specified metal or metal alloy composition
• CPC Class Codes: Y10S 977/896 : Chemical synthesis, e.g. chemical bonding or breaking
• CPC Class Codes: Y10S 977/92 : Detection of biochemical

Abstract

This application features a method of forming a nanoporous layer. The method includes steps of reducing metal ions in a reverse micelle phase composition to form nanoparticles, removing surfactant from the composition to form clusters of the nanoparticles, dispensing the composition including the nanoparticle clusters dispersed in a liquid on a substrate, and drying to form the nanoporous layer. The nanoporous layer includes nanoparticles deposited to form a three dimensional network of irregularly shaped bodies. The nanoporous layer also includes a three dimensional network of intercluster spaces that are not occupied by the three dimensional network of irregularly shaped bodies.

Claims

1. A method of making a nanoporous layer, the method comprising:

providing a liquid composition comprising a surfactant and metal ions, wherein the surfactant is in a reverse micelle phase comprising a plurality of hydrophilic spaces;

adding a reducing agent to the liquid composition to cause reduction of at least part of the metal ions to form nanoparticles, which provides a first colloid, wherein at least some of the hydrophilic spaces enclose at least one of the nanoparticles;

removing the surfactant from the first colloid to form a second colloid comprising nanoparticles from the first colloid such that the second colloid is substantially free of the surfactant, wherein removing the surfactant causes at least part of the nanoparticles to get together and form a number of nanoparticle clusters having an irregularly shaped body which comprises a number of nanoparticles having a generally oval or spherical shape with a length ranging between about 2 nm and about 5 nm;

subsequently, adjusting a concentration of the nanoparticles in the second colloid to provide a colloid composition such that the nanoparticles contained in the colloid composition are in an amount between about 0.01 wt % and about 2 wt % with reference to the total weight of the colloid composition;

dispensing, over a substrate, the colloid composition comprising nanoparticle clusters from the second colloid; and

subjecting the dispensed colloid composition to drying to form a nanoporous layer in which the nanoparticle clusters contained in the dispensed colloid composition deposit over the substrate such that irregularly shaped bodies of the nanoparticle clusters connect to one another to form a three-dimensional interconnected network of irregularly shaped bodies comprising a number of nanoparticles,

wherein the substrate comprises an electrically conductive or semiconductive surface, and the irregularly shaped bodies comprising a number of nanoparticles settle on the electrically conductive or semiconductive surface of the substrate.

2. The method of claim 1, wherein the nanoporous layer is substantially free of the surfactant such that the surfactant is in an amount smaller than 0.5 parts by weight with reference to 100 parts by weight of the nanoparticles contained in the nanoporous layer.

3. The method of claim 1, wherein the three-dimensional interconnected network of irregularly shaped bodies comprises numerous nanoparticles from the nanoparticle clusters of the colloid composition,

wherein, inside the three-dimensional interconnected network of irregularly shaped bodies, adjacent ones of the nanoparticles are apart from each other and form interparticular nanopores.

4. The method of claim 3, wherein the interparticular nanopores are distributed generally throughout in the three-dimensional interconnected network of irregularly shaped bodies.

5. The method of claim 3, wherein at least part of the interparticular nanopores inside the three-dimensional interconnected network of irregularly shaped bodies have an interparticular gap distance between two immediately neighboring nanoparticles, wherein the interparticular gap distance is within a range between about 0.5 nm and about 3 nm.

6. The method of claim 1, wherein the nanoporous layer comprises the three-dimensional interconnected network of irregularly shaped bodies and further comprises a three-dimensional interconnected network of irregularly shaped spaces that are not occupied by the three-dimensional interconnected network of irregularly shaped bodies.

7. The method of claim 6, wherein at least part of the irregularly shaped spaces of the three-dimensional interconnected network of irregularly shaped spaces comprises gaps in a size ranging between about 100 nm and about 500 nm.

8. The method of claim 1, further comprising, subsequent to adjusting the concentration and prior to dispensing, storing the colloid composition in a container for a period longer than a week.

9. The method of claim 1, wherein the substrate comprises an electrically conductive metal layer and an electrically conductive carbon layer formed on the electrically conductive metal layer, wherein the electrically conductive carbon layer provides the electrically conductive surface.

10. The method of claim 1, wherein the colloid composition is dispensed in a predetermined amount to form the nanoporous layer having roughness factor between about 100 and about 2500.

11. The method of claim 1, wherein no electric potential is applied for reduction of the at least part of the metal ions.

12. The method of claim 1, wherein to form the second colloid, the surfactant is removed from the first colloid such that the second colloid comprises the surfactant in an amount smaller than 2 parts by weight with reference to 100 parts by weight of the nanoparticles.

13. The method of claim 1, wherein some molecules of the surfactant are bound to nanoparticles in the first colloid, wherein removing the surfactant further comprises adding an acid or base to the first colloid to separate at least part of the surfactant from the nanoparticles.

14. The method of claim 1, wherein removing the surfactant comprises:

centrifuging the first colloid;

collecting a bottom portion from a centrifuged composition;

adding a solvent to the collected bottom portion; and

repeating a sequence of centrifuging the collected bottom portion with added solvent, collecting a bottom portion from its centrifuged composition, and adding the solvent thereto.

15. The method of claim 1, wherein each nanoparticle cluster has an irregularly shaped body comprising a number of nanoparticles having a generally oval or spherical shape with a length ranging between about 2 nm and about 5 nm.

16. The method of claim 1, wherein the irregularly shaped bodies are dispersed in a liquid and have a length ranging between about 50 nm and about 300 nm,

wherein a first one of the irregularly shaped bodies comprises a first nanoparticle and a second nanoparticle, each of which has a generally oval or spherical shape with a length ranging between about 2 nm and about 5 nm, wherein, inside the first irregularly shaped body, the first and second nanoparticles are adjacent to each other without an intervening nanoparticle therebetween and apart from each other with a first interparticular gap in a size ranging between about 0.5 nm to about 3 nm.

17. The method of claim 1, wherein subjecting the dispensed colloid composition to drying causes the irregularly shaped bodies from the dispensed colloid composition to deposit over the substrate such that adjacent ones of the irregularly shaped bodies abut one another at some surfaces or portions thereof while forming unoccupied spaces between non-abutting surfaces or portions of the adjacent ones of the irregularly shaped bodies.

18. The method of claim 17, wherein abutments between adjacent ones of the irregularly shaped bodies connect with one another, which continues to other ones of the irregularly shaped bodies to form the three-dimensional interconnected network of irregularly shaped bodies,

wherein, inside the three-dimensional interconnected network of irregularly shaped bodies, at least part of the nanoparticles are adjacent to each other without an intervening nanoparticle therebetween and apart from each other with interparticular nanopores therebetween.

19. The method of claim 17, wherein the unoccupied spaces between non-abutting surfaces or portions of the adjacent ones of the irregularly shaped bodies are irregularly shaped and connect with other unoccupied spaces formed by other ones of the irregularly shaped bodies,

wherein connections between the unoccupied spaces form the three-dimensional interconnected network of irregularly shaped spaces,

wherein the three-dimensional interconnected network of irregularly shaped spaces and the three-dimensional interconnected network of irregularly shaped bodies are complementary to form the nanoporous layer.

20. A method of making a glucose-sensing electrode, the method comprising:

the method of making a nanoporous layer according to claim 1;

forming an electrolyte ion-blocking layer over the nanoporous layer; and

wherein, when contacting a test liquid containing glucose, Na⁺, K⁺, Ca²⁺, Cl⁻

, PO₄³⁻

and CO₃²⁻

, the electrolyte ion-blocking layer is configured to inhibit Na⁺, K⁺, Ca²⁺, Cl⁻

, PO₄³⁻

and CO₃²⁻

contained in the test liquid from diffusing toward the nanoporous layer such that there is a substantial discontinuity of a combined concentration of Na⁺, K⁺, Ca²⁺, Cl⁻

, PO₄³⁻

and CO₃²⁻

between over the electrolyte ion-blocking layer and below the electrolyte ion-blocking layer.

21. The method of claim 20, wherein the substantial discontinuity of the combined concentration is such that combined concentration below the electrolyte ion-blocking layer is greater than 0% and lower than about 10% of the combined concentration above the electrolyte ion-blocking layer.

22. A method of making a glucose-sensing electrode, the method comprising:

the method of making a nanoporous layer according to claim 1;

forming a maltose-blocking layer over the nanoporous layer; and

forming the maltose-blocking layer comprising a poly-phenylenediamine (poly-PD) film over the nanoporous layer such that the poly-PD film has porosity to permit glucose to pass therethrough and to inhibit maltose from passing therethrough toward the nanoporous layer such that electric current caused by oxidation of glucose alone in the nanoporous layer is higher than 10 nA/mMcm² and further such that electric current caused by oxidation of maltose alone in the nanoporous layer is lower than 5 nA/mMcm², when a bias voltage of 0.2-0.45 V is applied to the nanoporous layer relative to a reference electrode and further when the poly-PD film contacts liquid containing glucose in a concentration of 4-20 mM and maltose in a concentration of 4-20 mM.