Nanoparticle sensor having a nanofibrous membrane scaffold

Patent metadata

Field	Value
Publication number	US-11331019-B2
Application number	US-201816057314-A
Country	US
Kind code	B2
Filing date	Aug 7, 2018
Priority date	Aug 7, 2017
Publication date	May 17, 2022
Grant date	May 17, 2022

Abstract

Nanoparticle-fibrous membrane composites are provided as tunable interfacial scaffolds for flexible chemical sensors and biosensors by assembling gold nanoparticles (Au NPs) in a fibrous membrane. The gold nanoparticles are functionalized with organic, polymeric and/or biological molecules. The fibrous membranes may include different filter papers, with one example featuring a multilayered fibrous membrane consisting of a cellulose nanofiber (CN) top layer, an electrospun polyacrylonitrile (PAN) nanofibrous midlayer (or alternate material), and a nonwoven polyethylene terephthalate (PET) fibrous support layer, with the nanoparticles provided on the fibrous membranes through interparticle molecular/polymeric linkages and nanoparticle-nanofibrous interactions. Molecular linkers may be employed to tune hydrogen bonding and electrostatic and/or hydrophobic/hydrophilic interactions to provide sensor specificity to gases or liquids. The sensors act as chemiresistor-type sensors. A preferred implementation is a sweat sensor.

First claim

What is claimed is:

1. A sensor, comprising:
a sensing medium, comprising a plurality of fibers within a fibrous layer, and a plurality of metallic nanoparticles coating the plurality of fibers within the fibrous layer, the plurality of metallic nanoparticles being derivatized to reversibly interact with the fibrous layer and a chemical analyte, based on at least one of electronic charge, ligand coordination, hydrogen bonding, van der Waals force, polarity, hydrophilicity, and hydrophobicity; and
an electrode, configured to sense a change in a state of the sensing medium over time responsive to the chemical analyte, and to produce an electrical signal output corresponding to the change in the state.

2. The sensor according to claim 1 , wherein the plurality of fibers within the fibrous layer comprise nanofibers.

3. The sensor according to claim 1 , wherein the plurality of fibers within the fibrous layer comprise nanofibrous cellulose.

4. The sensor according to claim 1 , wherein the plurality of fibers comprise a plurality of nanofibers, and the plurality of metallic nanoparticles are derivatized with an alkanethiolate shell.

5. The sensor according to claim 1 , wherein the fibrous layer comprises a natural cellulose fiber paper.

6. The sensor according to claim 1 , wherein the plurality of metallic nanoparticles are gold nanoparticles.

7. The sensor according to claim 1 , wherein the plurality of metallic nanoparticles are derivatized to be electronically charged.

8. The sensor according to claim 1 , further comprising a permeable electrospun fiber layer supporting the fibrous layer.

9. The sensor according to claim 1 , further comprising a permeable layer formed of fibers having a first diameter, and a non-woven fiber layer formed of fibers having a second diameter, the permeable layer being supported on the nonwoven fiber layer, and the fibrous layer being formed of fibers having a third diameter and being supported on the permeable layer,
wherein the second diameter is larger than the first diameter, and the first diameter larger than the third diameter.

10. The sensor according to claim 1 , further comprising:
a permeable layer comprising at least one polymer selected from the group consisting of crosslinked polyacrylonitrile (PAN) and crosslinked polyethylene glycol diacrylate (PEGDA); and
a polyethylene terephthalate (PET) non-woven layer,
the permeable layer being supported on the polyethylene terephthalate (PET) non-woven layer, and the fibrous layer being supported on the permeable layer.

11. The sensor according to claim 1 ,
wherein the fibrous layer consists essentially of fibers having a fiber diameter of between 1 nm and 15 nm,
the fibrous layer being supported on a fibrous intervening layer comprising fibers having a fiber diameter of between 50 nm and 250 nm, and
the fibrous intervening layer is disposed on a flexible support layer.

12. The sensor according to claim 1 , wherein the plurality of metallic nanoparticles are at least one of:
linked to a thiolate through a thiol bond;
linked to 11-mercaptoundecanoic acid (MUA) within the fibrous layer through a hydrogen bond;
linked to a carboxylic acid; and
electrostatically bound to poly(diallyl ammonium) within the fibrous layer.

13. The sensor according to claim 1 , wherein the fibrous layer is cast from a slurry of nanofibers on an electrospun layer.

14. The sensor according to claim 1 , wherein the electrical signal output is selectively responsive to a concentration of at least one of moisture and ions of the chemical analyte.

15. The sensor according to claim 1 , wherein the electrode comprises a pair of spaced interdigitated conductive traces separated by a gap, configured to sense a change in at least one of a conductivity and a capacitance of the fibrous layer, further comprising an electronic circuit configured to receive the electrical signal output, and to determine a quantitative parameter of the chemical analyte.

16. The sensor according to claim 1 , wherein the electrical signal output has a monotonically increasing electrical response to a concentration of an ionic species within the chemical analyte over a range from 0 to 100 mM.

17. A method of sensing chemical analyte, comprising:
providing a sensor, the sensor comprising:
a sensing medium comprising a fibrous layer and a plurality of derivatized conductive nanoparticles, the plurality of derivatized conductive nanoparticles coating fibers within the fibrous layer, and the derivatized conductive nanoparticles being derivatized to reversibly interact with the fibrous layer to alter an electrical state of the sensing medium in response to the chemical analyte, based on at least one of an electronic charge, hydrogen bonding, van der Waals force, polarity, hydrophilicity, and hydrophobicity of the derivatized conductive nanoparticles; and
an electrode for sensing a change in the electrical state of the sensing medium and producing as an output an electrical signal corresponding to the sensed change in electrical state;
exposing the sensor to the chemical analyte; and
producing the output, representing the sensed electrical state of the sensing medium dependent on the reversible interaction between the chemical analyte and the derivatized conductive nanoparticles.

18. The method according to claim 17 , wherein the fibers of the fibrous layer have a nanofiber diameter of between 1 nm and 15 nm, and have exposed groups capable of at least one of ionic bonding, hydrogen bonding, and van der Waals interaction with the derivatized conductive nanoparticles, and the derivatized conductive nanoparticles comprise gold nanoparticles having a diameter between 2 and 70 nm, derivatized to have at least one sulfur linkage.

19. A sensor, comprising:
a sensing medium, comprising a mat of nanofibers coated with derivatized conductive metallic nanoparticles, wherein the derivatized conductive metallic nanoparticles reversibly interact with the mat of fibers and a chemical analyte, based on at least one of electronic charge, ligand coordination, hydrogen bonding, van der Waals force, polarity, hydrophilicity, and hydrophobicity, to have an electrical impedance responsive to a concentration of the chemical analyte; and
an electrode, configured to sense a change in the electrical impedance of the sensing medium in response to a change in the concentration of the chemical analyte, and to conduct an electrical signal output in dependence on the electrical impedance,
wherein the nanofibers comprise organic nanofibers having a nanofiber diameter of between 1 nm and 100 nm, and the derivatized conductive metallic nanoparticles having a nanoparticle diameter of between 1 nm and 200 nm.

20. The sensor according to claim 19 , wherein:
the derivatized conductive metallic nanoparticles comprise gold nanoparticles having a diameter between 2 and 70 nm, derivatized to have sulfur linkages; and
the nanofibers comprise cellulose nanofibers,
wherein the chemical analyte is human sweat, and the sensor has an impedance which varies selectively responsive to a presence of the human sweat.

Assignees

• Univ New York State Res Found

Inventors

• Zhong Chuan-Jian
• Poliks Mark D
• Hsiao Benjamin S
• Kang Ning
• Yan Shan
• Li Jing
• Shan Shiyao
• Luo Jin

Classifications

• A61B2562/0285

  Nanoscale sensors · CPC title

• A61B5/1477 Primary

  non-invasive · CPC title

• A61B2560/0412

  Low-profile patch shaped housings · CPC title

• A61B5/145

  Measuring characteristics of blood in vivo, e.g. gas concentration or pH-value {; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid or cerebral tissue} (non-radiation detecting or locating of foreign bodies in blood A61B5/06) · CPC title

• A61B2562/0295

  Strip shaped analyte sensors for apparatus classified in A61B5/145 or A61B5/157 · CPC title