WO2022075549A1

WO2022075549A1 - Ph change sensing fiber, ph change sensing fabric, and ph change sensor comprising same

Info

Publication number: WO2022075549A1
Application number: PCT/KR2021/006985
Authority: WO
Inventors: 구형준; 김수영; 김지혜; 최민영
Original assignee: 서울과학기술대학교 산학협력단
Priority date: 2020-10-06
Filing date: 2021-06-04
Publication date: 2022-04-14
Also published as: KR102505025B1; KR20220045676A

Abstract

The present invention relates to a pH change sensing fiber, a pH change sensing fabric, and a pH change sensor comprising same, and the pH change sensing fiber according to one embodiment of the present invention comprises: a working electrode comprising, in a polymer matrix, a conductive filler and a pH-sensitive filler; and a reference electrode comprising a metal wire in a metal salt-polymer complex.

Description

PH change sensing fabric, PH change sensing fabric, and PH change sensing sensor comprising the same

The present invention relates to a pH change sensing fiber, a pH change sensing fabric, and a pH change sensing sensor comprising the same.

Accurate and reliable pH measurement can be important in fields ranging from chemical, biological and environmental analysis, food science, human health care and disease diagnosis. In particular, the importance of monitoring changes in the pH of body fluids such as tears, saliva, urine and sweat has increased as the demand for medical and diagnostic applications has rapidly increased.

For example, sweat excreted by a healthy person is slightly acidic at a pH of 4.5 to 6.5, while that of a patient with cystic fibrosis rises to a pH of 9. In addition, the skin that is usually slightly acidic (~ pH 6) returns to its original pH state after going through acidity and basicity in the process of wounding and healing. Furthermore, the salivary pH of patients with chronic periodontitis may be more alkaline compared to patients with clinically healthy dental tissue. Thus, the pH value of saliva can be important in determining dental health. In addition, the pH of urine may be associated with metabolic syndrome and health conditions associated with kidney disease.

For this reason, a pH sensor capable of more easily measuring the pH of an analyte sample such as a body fluid has been developed. Most pH sensors are based on a potentiometric electrode, an ion-sensitive field-effect transistor, and a chemo-resistor transistor. It has a form deposited on the surface of the substrate.

However, such a conventional pH sensor, it is difficult to effectively measure the pH of the distribution liquid due to its large volume or lack of flexibility. Film-type pH sensors are being developed, but there is a limit to having enough flexibility to adhere to the curves of the human body.

Accordingly, there is a continuous demand for the development of a new pH sensor that can solve the problems caused by the structural characteristics of the above-described conventional pH sensors and can more easily measure the pH of an analyte sample such as a body fluid.

The present invention is to solve the above-described problems, and an object of the present invention is to maximize skin adhesion by increasing flexibility, to easily measure changes in pH of body fluids, and to monitor health status and wound healing stages through this. To provide a pH change sensing fiber, a pH change sensing fabric, and a pH change sensing sensor including the same.

However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

The pH change sensing fiber according to an embodiment of the present invention comprises: a working electrode comprising a conductive filler and a pH-sensitive filler in a polymer matrix; and a reference electrode including a metal wire in the metal salt/polymer complex.

In one embodiment, the polymer matrix, agarose (agarose), alginate (alginate) and at least one biopolymer selected from the group consisting of gelatin (gelatin); Or polycaprolactone, polyvinyl alcohol, polylactic acid, poly m-aramid, polyurethane, polylactic acid-glycolide (Poly lactide-co-) glycolide), polyvinylidene fluoride, polyamide, polyimide, polyamide-imide, polysulfone, and polymethyl methacrylate It may include; at least one synthetic polymer selected from the group consisting of.

In one embodiment, the conductive filler includes a nanostructure including carbon, metal, and both, and the nanostructure is a nanosphere, a nanorod (NR), a nanowire, At least one selected from the group consisting of NW), nanowall, nanotube (NT), nanoribbon (NRB), nanobelt (NB) and nanosheet (NS) may include.

In one embodiment, the conductive filler, carbon fiber thread (carbon fiber thread), carbon black (carbon black), carbon graphite (carbon graphite), graphene (graphene), fullerene (fullerene), carbon nanotubes (carbon) nanotube), carbides, fullerene, and may include at least one selected from the group consisting of metal nanowires.

In one embodiment, the pH-sensitive filler, polyaniline (polyaniline), polypyrrole (polypyrrole), poly-N-methylpyrrole (poly-N-methylpyrrole), polythiophene (polythiopHene), poly (ethylenedioxythiophene) [poly(ethylenedioxythiopHene)], poly-3-methylthiopHene, poly(3,4-ethylenedioxythiophene) [poly(3,4-ethylenedioxythipHene); PEDOT], poly(p-phenylenevinylene)[poly(ppHenylenevinylene); PPV] and polyfuran (polyfuran) may include at least one selected from the group consisting of.

In one embodiment, the metal wire is a wire containing at least one metal selected from the group consisting of Ag, Au, Ni, Cu, Zn, Fe, Al, Ti, Pt, Hg and Pb, and Silver chloride may be coated on the metal wire.

In one embodiment, the metal salt / metal salt of the polymer complex is LiCl, NaCl, NaCN, KCl, KBr, KF, KCN, MgCl ₂ , MgBr ₂ , FeCl ₂ , NiCl ₂ , CuSO ₄ , Cu(Tos) ₂ , CuCl ₂ , CuBr ₂ , ZnCl ₂ , Ag ₂ SO ₄ , IrCl ₃ , H ₂ PtCl ₆ , AuCl ₃ and HgCl ₂ It will contain at least one selected from the group consisting of, the metal salt / polymer of the polymer composite, selected from the group consisting of polydimethylsiloxane (PDMS), polymethylphenylsiloxane, polymethylvinylsiloxane, polydiphenylsiloxane and poly(butylene-adipate-coterephthalate) It may be to include at least any one of.

In one embodiment, the working electrode and the reference electrode may have a twisted structure.

In the pH change sensing fabric according to another embodiment of the present invention, the pH change sensing fiber according to an embodiment of the present invention is woven into the fabric.

In one embodiment, the working electrode and the reference electrode may be woven into the fabric in a crossbar array structure.

A pH change sensor according to another embodiment of the present invention includes a pH change sensing fiber according to an embodiment of the present invention or a pH change sensing fabric according to another embodiment of the present invention.

In the pH change sensing fiber according to an embodiment of the present invention, by adding an oxide film-like polishing stopper, the oxide film polishing force is significantly lowered, and a high selectivity can be realized.

The pH change sensing fabric according to an embodiment of the present invention can be applied to clothes, wrist guards, smart bands, etc., so that it can be worn conveniently by increasing flexibility, and it can increase skin adhesion, so that the pH of the skin secretion can be measured more accurately there is. In addition, breathability is ensured, so that when applied to the human body, the wearing comfort can be improved.

The pH change sensor according to an embodiment of the present invention may be easy to handle, inexpensive, and have high electrical conductivity and flexibility. Accordingly, the present invention may be suitable as a wearable sensor, thereby contributing to the expansion of the application range of the pH sensor. Because it is possible to remotely monitor the health status and wound healing stage in real time and also two-dimensional pH mapping, it can provide various clinical information related to diseases and health conditions in medical and diagnostic applications, so it can be used in the bio/health care field It is expected to be of great value.

1 exemplarily shows a pH change sensing fiber according to an embodiment of the present invention.

2 is a view schematically showing the inside of the working electrode according to an embodiment of the present invention.

3 is a diagram schematically showing the inside of a reference electrode according to an embodiment of the present invention.

4 is a view schematically showing a pH change sensing fiber of a twisted structure according to an embodiment of the present invention.

5 is a view schematically showing a pH change sensing fabric according to an embodiment of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes may be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all modifications, equivalents and substitutes for the embodiments are included in the scope of the rights.

The terms used in the examples are used for the purpose of description only, and should not be construed as limiting. The singular expression includes the plural expression unless the context clearly dictates otherwise. In this specification, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, component, part, or a combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

In addition, in the description with reference to the accompanying drawings, the same components are given the same reference numerals regardless of the reference numerals, and the overlapping description thereof will be omitted. In describing the embodiment, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the embodiment, the detailed description thereof will be omitted.

In addition, in describing the components of the embodiment, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only for distinguishing the elements from other elements, and the essence, order, or order of the elements are not limited by the terms.

Components included in one embodiment and components having a common function will be described using the same names in other embodiments. Unless otherwise stated, descriptions described in one embodiment may be applied to other embodiments as well, and detailed descriptions within the overlapping range will be omitted.

The pH change sensing fiber according to an embodiment of the present invention has excellent pH sensing performance and excellent flexibility.

Referring to FIG. 1 , the pH change sensing fiber 100 according to an embodiment of the present invention includes a working electrode 110 and a reference electrode 120 .

In one embodiment, the working electrode 110 may mean a sensing electrode configured to measure the potential of the analyte sample in the pH sensor. In particular, the working electrode 110 contains a pH-sensitive filler whose potential changes depending on the concentration of hydrogen ions, so it may be configured to react directly/indirectly with an analysis sample for pH measurement.

In one embodiment, the pH change sensing fiber may have a different potential depending on the ion concentration of the analysis sample, and the analysis sample may mean any sample whose pH is to be measured. Preferably, the assay sample may be a fluid sample. For example, it may be cell lysate, whole blood, plasma, serum, saliva, ocular fluid, cerebrospinal fluid, sweat, urine, milk, ascites fluid, synovial fluid and peritoneal fluid. The sample may be lysed before being processed by the pH sensor of the present invention, depending on the type.

In an embodiment, the working electrode 110 may include a filler whose chemical properties change according to a change in pH in the polymer matrix 112 .

In one embodiment, the working electrode 110 is to include a conductive filler 114 capable of sensing a potential difference in the polymer matrix 112 and a pH-sensitive filler 116 whose potential changes according to pH. can

By this structural feature, the pH sensor of the present invention is configured to measure pH based on the potential difference with respect to the two working electrodes 110 and the reference electrode 120 .

In one embodiment, the polymer matrix 112 may include a polymer for fiber formation. The polymer matrix is not limited as long as it is a material capable of dissolving a polymer for fiber formation in a solvent to gel it while extruding the polymer sol, and drying it to produce a microcomposite fiber.

In one embodiment, the polymer matrix 112, agarose (agarose), alginate (alginate) and at least one biopolymer selected from the group consisting of gelatin (gelatin); Or polycaprolactone, polyvinyl alcohol, polylactic acid, poly m-aramid, polyurethane, polylactic acid-glycolide (Poly lactide-co-) glycolide), polyvinylidene fluoride, polyamide, polyimide, polyamide-imide, polysulfone, and polymethyl methacrylate It may include; at least one synthetic polymer selected from the group consisting of. Preferably, the matrix may be agarose (agarose).

In an embodiment, the conductive filler 114 includes a nanostructure including carbon, metal, and both, and the nanostructure includes a nanosphere, a nanorod (NR), a nanowire. (nanowire, NW), nanowall, nanotube (NT), nanoribbon (NRB), at least selected from the group consisting of nanobelt (NB) and nanosheet (NS) It may include any one.

In one embodiment, the conductive filler 114, carbon fiber thread (carbon fiber thread), carbon black (carbon black), carbon graphite (carbon graphite), graphene (graphene), fullerene (fullerene), carbon nano It may include at least one selected from the group consisting of a tube (carbon nanotube), carbides (carbides), fullerene (fullerene), and metal nanowires.

In one embodiment, the pH-sensitive filler 116, polyaniline (polyaniline), polypyrrole (polypyrrole), poly-N-methylpyrrole (poly-N-methylpyrrole), polythiophene (polythiopHene), poly (ethylenediox) thiophene) [poly(ethylenedioxythiopHene)], poly-3-methylthiopHene, poly(3,4-ethylenedioxythiophene) [poly(3,4-ethylenedioxythipHene); PEDOT], poly(p-phenylenevinylene)[poly(ppHenylenevinylene); PPV] and polyfuran (polyfuran) may include at least one selected from the group consisting of. Preferably, the pH-sensitive filler 116 may be polyaniline.

In one embodiment, each of the conductive filler 114 and the pH-sensitive filler 116 may perform two roles at the same time.

In one embodiment, the reference electrode 120 may mean a half-cell potential carbon cable having a stable potential to change in pH. Since the potential of the reference electrode 120 may be predetermined, when measuring the electromotive force or the electrode potential of the analyte sample through the working electrode 110, it may be used as a reference electrode that can be a reference.

In one embodiment, the reference electrode 120 may include a metal wire 124 in the metal salt/polymer composite 122 and silver chloride 126 coated on the metal wire.

In an embodiment, the metal salt of the metal salt/polymer complex 122 is LiCl, NaCl, NaCN, KCl, KBr, KF, KCN, MgCl ₂ , MgBr ₂ , FeCl ₂ , NiCl ₂ , CuSO ₄ , Cu(Tos) ) ₂ , CuCl ₂ , CuBr ₂ , ZnCl ₂ , Ag ₂ SO ₄ , IrCl ₃ , H ₂ PtCl ₆ , AuCl ₃ and HgCl ₂ At least one selected from the group consisting of may be included. Preferably, the metal salt of the metal salt/polymer complex may be KCl.

In one embodiment, the polymer of the metal salt / polymer complex 122,

selected from the group consisting of polydimethylsiloxane (PDMS), polymethylphenylsiloxane, polymethylvinylsiloxane, polydiphenylsiloxane and poly(butylene-adipate-coterephthalate) It may be to include at least any one of. Preferably, the polymer may be polydimethylsiloxane (PDMS).

Referring to FIG. 4 , the pH change sensing fiber having a twisted structure according to an embodiment of the present invention may have a structure in which the working electrode 110 and the reference electrode 120 are twisted.

In one embodiment, the fabric may include at least one selected from the group consisting of wool, linen, silk, polyester, nylon, olefin, acetate, rayon, and cotton.

Referring to FIG. 5 , the pH change sensing fabric 200 according to an embodiment of the present invention may be one in which the working electrode 110 and the reference electrode 120 are woven into the fabric 210 in a crossbar array structure. . Therefore, since the pH can be selectively read from the nine points where the working electrode 110 and the reference electrode 120 form the contact point A, it is possible to measure the pH according to the location.

In one embodiment, the pH change detection sensor may be coupled or connected to various devices applied in the art for detecting a pH change by additionally measuring a potential difference, for example, an electrochemical analyzer, and in addition to thermal , devices and electrodes for sensing and analyzing optical, electrical, chemical or physical detection signals may be further connected or disposed, but this specification will not specifically mention them.

In one embodiment, the pH change sensor may be added with equipment capable of monitoring the pH change in real time and performing two-dimensional pH mapping.

In one embodiment, the pH change sensor is a sensor to which an electrochemical technology is applied to quantitatively and/or qualitatively analyze pH by immersing a plurality of electrodes in a sample and measuring a potential difference, current, or alternating current impedance between electrodes can mean

In an embodiment, the pH change sensor may further include a dielectric material to reduce pH interference. For example, since the dielectric material is coated on the reference electrode, the reference electrode may have stability even when pH is changed.

In an embodiment, the pH change sensor may be coated with a non-conductive coating material such as a polymer or ceramic to prevent interference with the pH measurement in a region other than the portion exposed for pH measurement. By the coating layer of the coating material, it may be possible to protect the reference electrode from moisture, physical damage, and external environment.

As described above, although the embodiments have been described with reference to the limited drawings, those skilled in the art may apply various technical modifications and variations based on the above. For example, the described techniques are performed in an order different from the described method, and/or the described components of the system, structure, apparatus, circuit, etc. are combined or combined in a different form than the described method, or other components Or substituted or substituted by equivalents may achieve an appropriate result.

Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims

a working electrode comprising a conductive filler and a pH-sensitive filler in a polymer matrix; and

a reference electrode including a metal wire in a metal salt/polymer complex;

containing,

pH change sensing fiber.
The method of claim 1,

The polymer matrix is

at least one biopolymer selected from the group consisting of agarose, alginate, and gelatin; or

Polycaprolactone, Polyvinyl alcohol, Polylactic acid, Poly m-aramid, Polyurethane, Poly lactide-co-glycolide ), polyvinylidene fluoride, polyamide, polyimide, polyamide-imide, polysulfone, and polymethyl methacrylate. at least one synthetic polymer selected from the group;

which includes,

pH change sensing fiber.
The method of claim 1,

The conductive filler,

and nanostructures comprising carbon, metal, and both;

The nanostructure is, nanosphere, nanorod (nanorod, NR), nanowire (nanowire, NW), nanowall (nanowall), nanotube (nanotube, NT), nanoribbon (nanoribbon, NRB), nano Belts (nanobelt, NB) and nanosheets (nanosheet, NS) comprising at least one selected from the group consisting of,

Carbon fiber thread, carbon black, carbon graphite, graphene, fullerene, carbon nanotube, carbides, fullerene ) and at least one selected from the group consisting of metal nanowires,

pH change sensing fiber.
The method of claim 1,

The pH-sensitive filler,

Polyaniline, polypyrrole, poly-N-methylpyrrole, polythiopHene, poly(ethylenedioxythiophene) [poly(ethylenedioxythiopHene)], poly-3-methyl thiophene (poly-3-methylthiopHene), poly (3,4-ethylenedioxythiophene) [poly (3,4-ethylenedioxythipHene); PEDOT], poly(p-phenylenevinylene)[poly(ppHenylenevinylene); PPV] and polyfuran (polyfuran) comprising at least one selected from the group consisting of,

pH change sensing fiber.
The method of claim 1,

The metal wire is a wire containing at least one metal selected from the group consisting of Ag, Au, Ni, Cu, Zn, Fe, Al, Ti, Pt, Hg and Pb,

Silver chloride is coated on the metal wire,

pH change sensing fiber.
The method of claim 1,

The metal salt / metal salt of the polymer complex is LiCl, NaCl, NaCN, KCl, KBr, KF, KCN, MgCl 2 , MgBr 2 , FeCl 2 , NiCl 2 , CuSO 4 , Cu(Tos) 2 , CuCl 2 , CuBr 2 , ZnCl 2 , Ag 2 SO 4 , IrCl 3 , H 2 PtCl 6 , AuCl 3 and HgCl 2 Will include at least one selected from the group consisting of,

The polymer of the metal salt / polymer complex is,

selected from the group consisting of polydimethylsiloxane (PDMS), polymethylphenylsiloxane, polymethylvinylsiloxane, polydiphenylsiloxane and poly(butylene-adipate-coterephthalate) which includes at least any one of

pH change sensing fiber.
The method of claim 1,

The working electrode and the reference electrode will have a twisted structure with each other,

pH change sensing fiber.
The pH change sensing fabric in which the pH change sensing fiber of claim 1 is woven into the fabric.
9. The method of claim 8,

The pH change sensing fabric,

That the working electrode and the reference electrode are woven into the fabric in a crossbar array structure with each other,

pH change sensing fabric.
A pH change sensor comprising the pH change sensing fabric of claim 1 or the pH change sensing fabric of claim 8 .