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

Ph change sensing fiber, ph change sensing fabric, and ph change sensor comprising same Download PDF

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WO2022075549A1
WO2022075549A1 PCT/KR2021/006985 KR2021006985W WO2022075549A1 WO 2022075549 A1 WO2022075549 A1 WO 2022075549A1 KR 2021006985 W KR2021006985 W KR 2021006985W WO 2022075549 A1 WO2022075549 A1 WO 2022075549A1
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poly
change sensing
change
group
fabric
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PCT/KR2021/006985
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French (fr)
Korean (ko)
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구형준
김수영
김지혜
최민영
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서울과학기술대학교 산학협력단
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Publication of WO2022075549A1 publication Critical patent/WO2022075549A1/en

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/302Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301Reference electrodes
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/414Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/414Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4146Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS involving nanosized elements, e.g. nanotubes, nanowires
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/18Physical properties including electronic components

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • the salivary pH of patients with chronic periodontitis may be more alkaline compared to patients with clinically healthy dental tissue.
  • the pH value of saliva can be important in determining dental health.
  • the pH of urine may be associated with metabolic syndrome and health conditions associated with kidney disease.
  • pH sensors capable of more easily measuring the pH of an analyte sample such as a body fluid.
  • 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.
  • 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.
  • the pH change sensing fiber 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.
  • 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.
  • 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.
  • the conductive filler may include at least one selected from the group consisting of metal nanowires.
  • 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.
  • 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.
  • 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.
  • PDMS polydimethylsiloxane
  • PDMS
  • the working electrode and the reference electrode may have a twisted structure.
  • the pH change sensing fiber according to an embodiment of the present invention is woven into the fabric.
  • the working electrode and the reference electrode may be woven into the fabric in a crossbar array structure.
  • a pH change sensor 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.
  • 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.
  • FIG. 2 is a view schematically showing the inside of the working electrode according to an embodiment of the present invention.
  • FIG. 3 is a diagram schematically showing the inside of a reference electrode according to an embodiment of the present invention.
  • FIG. 4 is a view schematically showing a pH change sensing fiber of a twisted structure according to an embodiment of the present invention.
  • FIG. 5 is a view schematically showing a pH change sensing fabric according to an embodiment of the present invention.
  • the pH change sensing fiber 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.
  • the pH change sensing fiber according to an embodiment of the present invention has excellent pH sensing performance and excellent flexibility.
  • 1 exemplarily shows a pH change sensing fiber according to an embodiment of the present invention.
  • the pH change sensing fiber 100 includes a working electrode 110 and a reference electrode 120 .
  • the working electrode 110 may mean a sensing electrode configured to measure the potential of the analyte sample in the pH sensor.
  • 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.
  • 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.
  • the assay sample may be a fluid sample.
  • 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.
  • the working electrode 110 may include a filler whose chemical properties change according to a change in pH in the polymer matrix 112 .
  • FIG. 2 is a view schematically showing the inside of the working electrode according to an embodiment of the present invention.
  • 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.
  • 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 .
  • 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.
  • 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.
  • the matrix may be agarose (agarose).
  • 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.
  • 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.
  • 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.
  • the pH-sensitive filler 116 may be polyaniline.
  • each of the conductive filler 114 and the pH-sensitive filler 116 may perform two roles at the same time.
  • 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.
  • FIG. 3 is a diagram schematically showing the inside of a reference electrode according to an embodiment of the present invention.
  • 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.
  • 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.
  • 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.
  • the metal salt of the metal salt/polymer complex may be KCl.
  • the polymer of the metal salt / polymer complex 122 In one embodiment, the polymer of the metal salt / polymer complex 122,
  • the polymer may be polydimethylsiloxane (PDMS).
  • the working electrode and the reference electrode may have a twisted structure.
  • FIG. 4 is a view schematically showing a pH change sensing fiber of a twisted structure according to an embodiment of the present invention.
  • the pH change sensing fiber having a twisted structure may have a structure in which the working electrode 110 and the reference electrode 120 are twisted.
  • the pH change sensing fiber according to an embodiment of the present invention is woven into the fabric.
  • the fabric may include at least one selected from the group consisting of wool, linen, silk, polyester, nylon, olefin, acetate, rayon, and cotton.
  • FIG. 5 is a view schematically showing a pH change sensing fabric according to an embodiment of the present invention.
  • the pH change sensing fabric 200 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.
  • 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.
  • a pH change sensor 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.
  • 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.
  • the pH change sensor may be added with equipment capable of monitoring the pH change in real time and performing two-dimensional pH mapping.
  • 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
  • the pH change sensor may further include a dielectric material to reduce pH interference.
  • the reference electrode since the dielectric material is coated on the reference electrode, the reference electrode may have stability even when pH is changed.
  • 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.
  • a non-conductive coating material such as a polymer or ceramic
  • 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.

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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 변화 감지 섬유, PH 변화 감지 직물 및 이를 포함하는 PH 변화 감지 센서PH change sensing fabric, PH change sensing fabric, and PH change sensing sensor comprising the same
본 발명은 pH 변화 감지 섬유, pH 변화 감지 직물 및 이를 포함하는 pH 변화 감지 센서에 관한 것이다.The present invention relates to a pH change sensing fiber, a pH change sensing fabric, and a pH change sensing sensor comprising the same.
정확하고 신뢰할 수 있는 pH 측정은, 화학, 생물 및 환경 분석, 식품 과학, 인간 건강 관리 및 질병 진단에 이르는 다양한 분야에서 중요할 수 있다. 특히, 의료 및 진단 응용 분야에 대한 수요가 급격히 증가함에 따라 눈물, 타액, 소변 및 땀과 같은 체액(Body fluid)의 pH 변화를 모니터링하는 것에 대한 중요도가 증가되었다.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.
예를 들어, 건강한 사람이 배출하는 땀은 pH 4.5에서 6.5의 약산성을 띄는 반면 낭포성 섬유증(Cystic Fibrosis)을 가진 환자의 땀은 pH 9까지 상승한다. 또한, 평소에 약한 산성(~ pH 6)을 띄는 피부는 상처가 나고 치유되는 과정에서 산성과 염기성을 거쳐 다시 원래의 pH 상태로 돌아온다. 나아가, 만성 치주염 환자의 타액 pH는 임상적으로 건강한 치아 조직을 갖는 환자에 비하여 더 알칼리성일 수 있다. 이에 타액의 pH 값은 치아 건강을 결정하는 것에 있어 중요할 수 있다. 또한, 소변의 pH는 대사 증후군 및 신장 질환과 관련된 건강 상태와 연관될 수 있다. 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.
이와 같은 이유로, 체액과 같은 분석 시료의 pH를 보다 용이하게 측정할 수 있는 pH 센서가 개발되고 있다. 대부분의 pH 센서들은, 전위차 전극(potentiometric electrode), 이온 감음성 전계 효과 트랜지스터(ion-sensitive field-effect transistor), 화학 저항성 트랜지스터(chemo-resistor transistor)를 기반으로 pH를 측정하기 위해, 금 박막이 기판의 표면에 증착된 형태를 갖는다.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.
그러나, 이러한 종래의 pH 센서는, 부피가 크거나 유연성이 떨어져 분배액의 pH를 효과적으로 측정하는데 어려움이 있다. 필름형 pH 센서가 개발되고 있으나 인체가 가지는 굴곡에 밀착될 수 있을 정도의 유연성을 갖는데에는 한계가 있다.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.
이에, 전술한 종래의 pH 센서들의 구조적 특성에 의해 야기되는 문제점들을 해결하고, 보다 용이하게 체액과 같은 분석 시료의 pH를 측정할 수 있는, 새로운 pH 센서의 개발이 지속적으로 요구되고 있는 실정이다.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.
본 발명은 상술한 문제점을 해결하기 위한 것으로, 본 발명의 목적은, 유연성을 높여 피부 밀착도를 극대화하고, 체액의 pH 변화를 쉽게 측정하고, 이를 통해 건강상태 및 상처치유 단계 등을 모니터링할 수 있는 pH 변화 감지 섬유, pH 변화 감지 직물 및 이를 포함하는 pH 변화 감지 센서를 제공하는 것이다.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.
그러나, 본 발명이 해결하고자 하는 과제는 이상에서 언급한 것들로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 해당 분야 통상의 기술자에게 명확하게 이해될 수 있을 것이다.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.
본 발명의 일 실시예에 따른 pH 변화 감지 섬유는, 고분자 매트릭스 내에 전도성 충진제 및 pH 감응 충진제를 포함하는 작동전극; 및 금속염/고분자 복합체 내에 금속 전선을 포함하는 기준전극;을 포함한다.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.
일 실시형태에 있어서, 상기 고분자 매트릭스는, 아가로즈(agarose), 알지네이트(alginate) 및 젤라틴(gelatin)로 이루어진 군으로부터 선택되는 적어도 어느 하나의 생체 고분자; 또는 폴리카프로락톤(Polycaprolactone), 폴리비닐알콜(Polyvinyl alchohol), 폴리락트산 (Polylactic acid), 폴리 메타 아라미드(Poly m-aramid), 폴리우레탄(Polyurethane), 폴리락트산-글리콜라이드(Poly lactide-co-glycolide), 폴리비닐리딘 플루오라이드(Polyvinylidene fluoride), 폴리아마이드(Polyamide), 폴리이미드(Polyimide), 폴리아마이드이미드 (Polyamide-imide), 폴리설폰(Polysulfone) 및 폴리메틸메타크릴레이트(Polymethyl Methacrylate)로 이루어진 군으로부터 선택되는 적어도 어느 하나의 합성 고분자;를 포함하는 것일 수 있다.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.
일 실시형태에 있어서, 상기 전도성 충진제는, 탄소, 금속 및 이 둘을 포함하는 나노구조를 포함하고, 상기 나노구조는, 나노구(nanosphere), 나노로드(nanorod, NR), 나노선(nanowire, NW), 나노벽(nanowall), 나노튜브(nanotube, NT), 나노리본(nanoribbon, NRB), 나노벨트(nanobelt, NB) 및 나노시트(nanosheet, NS)로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것일 수 있다.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.
일 실시형태에 있어서, 상기 전도성 충진제는, 카본 파이버 가닥(carbon fiber thread), 카본 블랙(carbon black), 카본 그래파이트(carbon graphite), 그래핀(graphene), 풀러렌(fullerene), 카본 나노튜브(carbon nanotube), 카바이드(carbides), 풀러렌(fullerene) 및 금속 나노선으로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것일 수 있다.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.
일 실시형태에 있어서, 상기 pH 감응 충진제는, 폴리아닐린(polyaniline), 폴리피롤(polypyrrole), 폴리-N-메틸피롤(poly-N-methylpyrrole), 폴리티오펜(polythiopHene), 폴리(에틸렌디옥시티오펜)[poly(ethylenedioxythiopHene)], 폴리-3-메틸티오펜(poly-3-methylthiopHene), 폴리(3,4-에틸렌디옥시티오펜)[poly(3,4-ethylenedioxythipHene); PEDOT], 폴리(p-페닐렌비닐렌)[poly(ppHenylenevinylene); PPV] 및 폴리퓨란(polyfuran)으로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것일 수 있다.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.
일 실시형태에 있어서, 상기 금속 전선은, Ag, Au, Ni, Cu, Zn, Fe, Al, Ti, Pt, Hg 및 Pb로 이루어진 군으로부터 선택되는 적어도 어느 하나의 금속을 포함하는 전선이고, 상기 금속 전선 상에 염화은이 코팅된 것일 수 있다.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.
일 실시형태에 있어서, 상기 금속염/고분자 복합체의 금속염은, LiCl, NaCl, NaCN, KCl, KBr, KF, KCN, MgCl2, MgBr2, FeCl2, NiCl2, CuSO4, Cu(Tos)2, CuCl2, CuBr2, ZnCl2, Ag2SO4, IrCl3, H2PtCl6, AuCl3 및 HgCl2로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것이고, 상기 금속염/고분자 복합체의 고분자는, 폴리디메틸실록산(polydimethylsiloxane; PDMS), 폴리메틸페닐실록산, 폴리메틸비닐실록산, 폴리디페닐실록산 및 폴리(부틸렌-아디페이트-코테레프탈레이트)(poly(butylene-adipate-coterephthalate))로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것일 수 있다.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.
일 실시형태에 있어서, 상기 작동전극 및 상기 기준전극은 서로 꼬인 구조를 가지는 것일 수 있다.In one embodiment, the working electrode and the reference electrode may have a twisted structure.
본 발명의 다른 실시예에 따른 pH 변화 감지 직물은, 본 발명의 일 실시예에 따른 pH 변화 감지 섬유가 직물에 직조된 것이다.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.
일 실시형태에 있어서, 상기 직물에 작동전극 및 기준전극이 서로 크로스바 어레이 구조로 직조된 것일 수 있다.In one embodiment, the working electrode and the reference electrode may be woven into the fabric in a crossbar array structure.
본 발명의 또 다른 실시예에 따른 pH 변화 감지 센서는, 본 발명의 일 실시예에 따른 pH 변화 감지 섬유 또는 본 발명의 다른 실시예에 따른 pH 변화 감지 직물을 포함한다.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.
본 발명의 일 실시예에 따른 pH 변화 감지 섬유는, 산화막질 연마 정지제를 첨가함으로써, 산화막 연마력을 크게 낮춰, 높은 선택비 구현 가능하다.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.
본 발명의 일 실시예에 따른 pH 변화 감지 직물은 의류, 손목 보호대, 스마트 밴드와 같은 곳에 적용함으로써 유연성을 높여 간편하게 착용할 수 있고, 피부밀착도를 높일 수 있어 피부 분비액의 pH를 보다 정확하게 측정할 수 있다. 또한, 통기성이 확보되어 인체에 적용 시 착용감을 향상시킬 수 있다.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.
본 발명의 일 실시예에 따른 pH 변화 감지 센서는 다루기 용이하고, 가격이 저렴하며, 높은 전기 전도성 및 유연성을 가질 수 있다. 이에, 본 발명은 웨어러블 센서로서 적합할 수 있음에 따라, pH 센서의 적용 범위 확장에 기여할 수 있다. 건강상태 및 상처치유 단계를 실시간으로 원격 모니터링하고 2차원 pH 매핑도 가능하므로, 의료 및 진단 응용 분야에서, 질환 및 건강 상태와 연관된 다양한 임상적 정보를 제공할 수 있어, 바이오/헬스케어 분야에 활용 가치가 매우 클 것으로 예상된다.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.
도 1은 본 발명의 일 실시예에 따른 pH 변화 감지 섬유를 예시적으로 도시한 것이다.1 exemplarily shows a pH change sensing fiber according to an embodiment of the present invention.
도 2는 본 발명의 일 실시예에 따른 작동전극 내부를 개략적으로 나타낸 도면이다.2 is a view schematically showing the inside of the working electrode according to an embodiment of the present invention.
도 3은 본 발명의 일 실시예에 따른 기준전극 내부를 개략적으로 나타낸 도면이다.3 is a diagram schematically showing the inside of a reference electrode according to an embodiment of the present invention.
도 4는 본 발명의 일 실시예에 따른 꼬인 구조의 pH 변화 감지 섬유를 개략적으로 나타낸 도면이다.4 is a view schematically showing a pH change sensing fiber of a twisted structure according to an embodiment of the present invention.
도 5는 본 발명의 일 실시예에 따른 pH 변화 감지 직물을 개략적으로 나타낸 도면이다.5 is a view schematically showing a pH change sensing fabric according to an embodiment of the present invention.
이하에서, 첨부된 도면을 참조하여 실시예들을 상세하게 설명한다. 그러나, 실시예들에는 다양한 변경이 가해질 수 있어서 특허출원의 권리 범위가 이러한 실시예들에 의해 제한되거나 한정되는 것은 아니다. 실시예들에 대한 모든 변경, 균등물 내지 대체물이 권리 범위에 포함되는 것으로 이해되어야 한다.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.
실시예에서 사용한 용어는 단지 설명을 목적으로 사용된 것으로, 한정하려는 의도로 해석되어서는 안된다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서, "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.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.
다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 실시예가 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.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
또한, 첨부 도면을 참조하여 설명함에 있어, 도면 부호에 관계없이 동일한 구성 요소는 동일한 참조부호를 부여하고 이에 대한 중복되는 설명은 생략하기로 한다. 실시예를 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 실시예의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다. 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.
또한, 실시 예의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a), (b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다.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.
어느 하나의 실시 예에 포함된 구성요소와, 공통적인 기능을 포함하는 구성요소는, 다른 실시 예에서 동일한 명칭을 사용하여 설명하기로 한다. 반대되는 기재가 없는 이상, 어느 하나의 실시 예에 기재한 설명은 다른 실시 예에도 적용될 수 있으며, 중복되는 범위에서 구체적인 설명은 생략하기로 한다.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.
본 발명의 일 실시예에 따른 pH 변화 감지 섬유는, 고분자 매트릭스 내에 전도성 충진제 및 pH 감응 충진제를 포함하는 작동전극; 및 금속염/고분자 복합체 내에 금속 전선을 포함하는 기준전극;을 포함한다.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.
본 발명의 일 실시예에 따른 pH 변화 감지 섬유는, pH 감지 성능이 우수하고, 유연성이 우수하다.The pH change sensing fiber according to an embodiment of the present invention has excellent pH sensing performance and excellent flexibility.
도 1은 본 발명의 일 실시예에 따른 pH 변화 감지 섬유를 예시적으로 도시한 것이다.1 exemplarily shows a pH change sensing fiber according to an embodiment of the present invention.
도 1을 참조하면, 본 발명의 일 실시예에 따른 pH 변화 감지 섬유(100)는 작동전극(110) 및 기준전극(120)을 포함한다.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 .
일 실시형태에 있어서, 상기 작동전극(110)은, pH 센서 내에서 분석 시료의 전위를 측정하도록 구성된 센싱 전극을 의미할 수 있다. 특히, 작동전극(110)은 수소 이온 농도 의존적으로 전위가 바뀌는 pH 감응 충진제가 내포되어 있어, pH 측정을 위해 분석 시료와 직/간접적으로 반응하도록 구성될 수 있다.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.
일 실시형태에 있어서, 상기 pH 변화 감지 섬유는 분석 시료의 이온 농도에 따라 상이한 전위를 가질 수 있으며, 분석 시료는 pH를 측정하고자 하는 모든 시료를 의미할 수 있다. 바람직하게, 분석 시료는 유체 시료일 수 있다. 예를 들어, 세포 용해물, 전혈, 혈장, 혈청, 침, 안구액, 뇌척수액, 땀, 뇨, 젖, 복수액, 활액 및 복막액일 수 있다. 상기 시료는, 그 종류에 따라 본 발명의 pH 센서에 처리되기 전에 용해(lysis) 될 수도 있다.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.
일 실시형태에 있어서, 상기 작동전극(110)은, 고분자 매트릭스(112)에 pH 변화에 따라 화학적 성질이 바뀌는 충진제(filler)를 포함하는 것일 수 있다.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 .
도 2는 본 발명의 일 실시예에 따른 작동전극 내부를 개략적으로 나타낸 도면이다.2 is a view schematically showing the inside of the working electrode according to an embodiment of the present invention.
일 실시형태에 있어서, 상기 작동전극(110)은, 고분자 매트릭스(112) 내에 전위차를 감지할 수 있게 해주는 전도성 충진제(114) 및 pH에 따라 전위가 변화하는 pH 감응 충진제(116)를 포함하는 것일 수 있다.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
이러한 구조적 특징에 의해, 본 발명의 pH 센서는, 두 개의 작동전극(110) 및 기준전극(120)에 대한 전위차를 기초로 pH를 측정할 수 있도록 구성된다.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 .
일 실시형태에 있어서, 상기 고분자 매트릭스(112)는 섬유 형성용 고분자를 포함하는 것일 수 있다. 상기 고분자 매트릭스는 섬유 형성용 고분자를 용매에 용해하여 고분자 졸을 압출하면서 젤화시켜 고분자 수화젤 섬유를 만들고, 이를 건조시켜 마이크로 복합체 섬유로 제조할 수 있는 소재라면 제한되지 않는다. 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.
일 실시형태에 있어서, 상기 고분자 매트릭스(112)는, 아가로즈(agarose), 알지네이트(alginate) 및 젤라틴(gelatin)로 이루어진 군으로부터 선택되는 적어도 어느 하나의 생체 고분자; 또는 폴리카프로락톤(Polycaprolactone), 폴리비닐알콜(Polyvinyl alchohol), 폴리락트산 (Polylactic acid), 폴리 메타 아라미드(Poly m-aramid), 폴리우레탄(Polyurethane), 폴리락트산-글리콜라이드(Poly lactide-co-glycolide), 폴리비닐리딘 플루오라이드(Polyvinylidene fluoride), 폴리아마이드(Polyamide), 폴리이미드(Polyimide), 폴리아마이드이미드 (Polyamide-imide), 폴리설폰(Polysulfone) 및 폴리메틸메타크릴레이트(Polymethyl Methacrylate)로 이루어진 군으로부터 선택되는 적어도 어느 하나의 합성 고분자;를 포함하는 것일 수 있다. 바람직하게는, 상기 매트릭스는, 아가로즈(agarose)를 사용하는 것일 수 있다.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).
일 실시형태에 있어서, 상기 전도성 충진제(114)는, 탄소, 금속 및 이 둘을 포함하는 나노구조를 포함하고, 상기 나노구조는, 나노구(nanosphere), 나노로드(nanorod, NR), 나노선(nanowire, NW), 나노벽(nanowall), 나노튜브(nanotube, NT), 나노리본(nanoribbon, NRB), 나노벨트(nanobelt, NB) 및 나노시트(nanosheet, NS)로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것일 수 있다.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.
일 실시형태에 있어서, 상기 전도성 충진제(114)는, 카본 파이버 가닥(carbon fiber thread), 카본 블랙(carbon black), 카본 그래파이트(carbon graphite), 그래핀(graphene), 풀러렌(fullerene), 카본 나노튜브(carbon nanotube), 카바이드(carbides), 풀러렌(fullerene) 및 금속 나노선으로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것일 수 있다.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.
일 실시형태에 있어서, 상기 pH 감응 충진제(116)는, 폴리아닐린(polyaniline), 폴리피롤(polypyrrole), 폴리-N-메틸피롤(poly-N-methylpyrrole), 폴리티오펜(polythiopHene), 폴리(에틸렌디옥시티오펜)[poly(ethylenedioxythiopHene)], 폴리-3-메틸티오펜(poly-3-methylthiopHene), 폴리(3,4-에틸렌디옥시티오펜)[poly(3,4-ethylenedioxythipHene); PEDOT], 폴리(p-페닐렌비닐렌)[poly(ppHenylenevinylene); PPV] 및 폴리퓨란(polyfuran)으로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것일 수 있다. 바람직하게는, 상기 pH 감응 충진제(116)는 폴리아닐린인 것일 수 있다.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.
일 실시형태에 있어서, 상기 전도성 충진제(114) 및 pH 감응 충진제(116) 각각은 두 가지 역할을 동시에 수행할 수도 있다.In one embodiment, each of the conductive filler 114 and the pH-sensitive filler 116 may perform two roles at the same time.
일 실시형태에 있어서, 상기 기준전극(120)은 pH변화에 안정적 전위를 갖는 반쪽 전지 전위성 탄소 케이블을 의미할 수 있다. 이러한 기준전극(120)의 전위는 미리 결정되어 있을 수 있음에 따라, 작동전극(110)을 통해 분석 시료의 기전력 또는 전극 전위를 측정할 때, 기준이 될 수 있는 기준 전극으로 이용될 수 있다.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.
도 3은 본 발명의 일 실시예에 따른 기준전극 내부를 개략적으로 나타낸 도면이다.3 is a diagram schematically showing the inside of a reference electrode according to an embodiment of the present invention.
일 실시형태에 있어서, 상기 금속 전선은, Ag, Au, Ni, Cu, Zn, Fe, Al, Ti, Pt, Hg 및 Pb로 이루어진 군으로부터 선택되는 적어도 어느 하나의 금속을 포함하는 전선이고, 상기 금속 전선 상에 염화은이 코팅된 것일 수 있다.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.
일 실시형태에 있어서, 상기 기준전극(120)은 금속염/고분자 복합체(122) 내에 금속 전선(124), 상기 금속 전선 상에 코팅된 염화은(126)을 포함하는 것일 수 있다.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.
일 실시형태에 있어서, 상기 금속염/고분자 복합체(122)의 금속염은, LiCl, NaCl, NaCN, KCl, KBr, KF, KCN, MgCl2, MgBr2, FeCl2, NiCl2, CuSO4, Cu(Tos)2, CuCl2, CuBr2, ZnCl2, Ag2SO4, IrCl3, H2PtCl6, AuCl3 및 HgCl2로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것일 수 있다. 바람직하게는, 상기 금속염/고분자 복합체의 금속염은, KCl인 것일 수 있다.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.
일 실시형태에 있어서, 상기 금속염/고분자 복합체(122)의 고분자는, In one embodiment, the polymer of the metal salt / polymer complex 122,
폴리디메틸실록산(polydimethylsiloxane; PDMS), 폴리메틸페닐실록산, 폴리메틸비닐실록산, 폴리디페닐실록산 및 폴리(부틸렌-아디페이트-코테레프탈레이트)(poly(butylene-adipate-coterephthalate))로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것일 수 있다. 바람직하게는, 상기 고분자는 폴리디메틸실록산(PDMS)인 것일 수 있다.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).
일 실시형태에 있어서, 상기 작동전극 및 상기 기준전극은 서로 꼬인 구조를 가지는 것일 수 있다.In one embodiment, the working electrode and the reference electrode may have a twisted structure.
도 4는 본 발명의 일 실시예에 따른 꼬인 구조의 pH 변화 감지 섬유를 개략적으로 나타낸 도면이다.4 is a view schematically showing a pH change sensing fiber of a twisted structure according to an embodiment of the present invention.
도 4를 참조하면, 본 발명의 일 실시예에 따른 꼬인 구조의 pH 변화 감지 섬유는 작동전극(110) 및 기준전극(120)이 꼬인 형태의 구조를 가질 수 있다.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.
본 발명의 다른 실시예에 따른 pH 변화 감지 직물은, 본 발명의 일 실시예에 따른 pH 변화 감지 섬유가 직물에 직조된 것이다.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.
일 실시형태에 있어서, 상기 직물은 양모, 리넨, 실크, 폴리에스테르, 나일론, 올레핀, 아세테이트, 레이온 및 면으로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것일 수 있다.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.
도 5는 본 발명의 일 실시예에 따른 pH 변화 감지 직물을 개략적으로 나타낸 도면이다.5 is a view schematically showing a pH change sensing fabric according to an embodiment of the present invention.
도 5를 참조하면, 본 발명의 일 실시예에 따른 pH 변화 감지 직물(200)은, 직물(210)에 작동전극(110) 및 기준전극(120)이 서로 크로스바 어레이 구조로 직조된 것일 수 있다. 따라서, 작동전극(110) 및 기준전극(120)이 접점(A)을 이루는 지점 9군데에서 pH를 선택적으로 읽어 들일 수 있어 위치에 따른 pH 측정이 가능할 수 있다.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.
본 발명의 일 실시예에 따른 pH 변화 감지 직물은 의류, 손목 보호대, 스마트 밴드와 같은 곳에 적용함으로써 유연성을 높여 간편하게 착용할 수 있고, 피부밀착도를 높일 수 있어 피부 분비액의 pH를 보다 정확하게 측정할 수 있다. 또한, 통기성이 확보되어 인체에 적용 시 착용감을 향상시킬 수 있다.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.
본 발명의 또 다른 실시예에 따른 pH 변화 감지 센서는, 본 발명의 일 실시예에 따른 pH 변화 감지 섬유 또는 본 발명의 다른 실시예에 따른 pH 변화 감지 직물을 포함한다.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.
일 실시형태에 있어서, 상기 pH 변화 감지 센서는 추가적으로 전위차를 측정하여 pH 변화를 검출하기 위한 본 발명의 기술분야에서 적용되는 다양한 장치, 예를 들어, 전기화학적 분석기가 결합 또는 연결될 수 있고, 이외에도 열적, 광학적, 전기적, 화학적 또는 물리적 검출신호를 감지 및 분석을 위한 장치 및 전극 등이 더 연결 또는 배치될 수 있으나, 본 명세서는 구체적으로 언급하지 않는다.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.
일 실시형태에 있어서, 상기 pH 변화 감지 센서는 pH 변화를 실시간으로 모니터링하고 2차원 pH 매핑도 가능한 장비가 추가될 수 있다.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.
일 실시형태에 있어서, 상기 pH 변화 감지 센서는 시료 중에 복수의 전극을 침지시켜, 전극 간 전위차, 전류 또는 교류 임피던스를 측정함으로써 정량적으로 및/또는 정성적으로 pH를 분석하는 전기 화학적 기술이 적용된 센서를 의미할 수 있다.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
일 실시형태에 있어서, 상기 pH 변화 감지 센서는, pH의 간섭을 줄이기 위하여 유전 물질을 더 포함할 수 있다. 예를 들어, 기준전극 상에 유전성 물질이 코팅됨으로써, 기준전극은 pH의 변화에도 안정성을 가질 수 있다.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.
일 실시형태에 있어서, 상기 pH 변화 감지 센서는, pH 측정을 위해 노출된 부분 이외에 영역에는, pH 측정의 간섭 방지를 위해 폴리머, 세라믹과 같은 부전도체의 피복 물질이 코팅되어 있을 수 있다. 이러한 피복 물질 코팅층에 의해, 수분, 물리적 손상, 외부 환경으로부터 기준전극의 보호가 가능할 수 있다.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.
본 발명의 일 실시예에 따른 pH 변화 감지 센서는 다루기 용이하고, 가격이 저렴하며, 높은 전기 전도성 및 유연성을 가질 수 있다. 이에, 본 발명은 웨어러블 센서로서 적합할 수 있음에 따라, pH 센서의 적용 범위 확장에 기여할 수 있다. 건강상태 및 상처치유 단계를 실시간으로 원격 모니터링하고 2차원 pH 매핑도 가능하므로, 의료 및 진단 응용 분야에서, 질환 및 건강 상태와 연관된 다양한 임상적 정보를 제공할 수 있어, 바이오/헬스케어 분야에 활용 가치가 매우 클 것으로 예상된다.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.
이상과 같이 실시예들이 비록 한정된 도면에 의해 설명되었으나, 해당 기술분야에서 통상의 지식을 가진 자라면 상기를 기초로 다양한 기술적 수정 및 변형을 적용할 수 있다. 예를 들어, 설명된 기술들이 설명된 방법과 다른 순서로 수행되거나, 및/또는 설명된 시스템, 구조, 장치, 회로 등의 구성요소들이 설명된 방법과 다른 형태로 결합 또는 조합되거나, 다른 구성요소 또는 균등물에 의하여 대치되거나 치환되더라도 적절한 결과가 달성될 수 있다.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.
그러므로, 다른 구현들, 다른 실시예들 및 특허청구범위와 균등한 것들도 후술하는 청구범위의 범위에 속한다.Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (10)

  1. 고분자 매트릭스 내에 전도성 충진제 및 pH 감응 충진제를 포함하는 작동전극; 및a working electrode comprising a conductive filler and a pH-sensitive filler in a polymer matrix; and
    금속염/고분자 복합체 내에 금속 전선을 포함하는 기준전극;a reference electrode including a metal wire in a metal salt/polymer complex;
    을 포함하는, containing,
    pH 변화 감지 섬유.pH change sensing fiber.
  2. 제1항에 있어서,The method of claim 1,
    상기 고분자 매트릭스는, The polymer matrix is
    아가로즈(agarose), 알지네이트(alginate) 및 젤라틴(gelatin)로 이루어진 군으로부터 선택되는 적어도 어느 하나의 생체 고분자; 또는at least one biopolymer selected from the group consisting of agarose, alginate, and gelatin; or
    폴리카프로락톤(Polycaprolactone), 폴리비닐알콜(Polyvinyl alchohol), 폴리락트산 (Polylactic acid), 폴리 메타 아라미드(Poly m-aramid), 폴리우레탄(Polyurethane), 폴리락트산-글리콜라이드(Poly lactide-co-glycolide), 폴리비닐리딘 플루오라이드(Polyvinylidene fluoride), 폴리아마이드(Polyamide), 폴리이미드(Polyimide), 폴리아마이드이미드 (Polyamide-imide), 폴리설폰(Polysulfone) 및 폴리메틸메타크릴레이트(Polymethyl Methacrylate)로 이루어진 군으로부터 선택되는 적어도 어느 하나의 합성 고분자;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;
    를 포함하는 것인, which includes,
    pH 변화 감지 섬유.pH change sensing fiber.
  3. 제1항에 있어서,The method of claim 1,
    상기 전도성 충진제는, The conductive filler,
    탄소, 금속 및 이 둘을 포함하는 나노구조를 포함하고,and nanostructures comprising carbon, metal, and both;
    상기 나노구조는, 나노구(nanosphere), 나노로드(nanorod, NR), 나노선(nanowire, NW), 나노벽(nanowall), 나노튜브(nanotube, NT), 나노리본(nanoribbon, NRB), 나노벨트(nanobelt, NB) 및 나노시트(nanosheet, NS)로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것이거나, 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,
    카본 파이버 가닥(carbon fiber thread), 카본 블랙(carbon black), 카본 그래파이트(carbon graphite), 그래핀(graphene), 풀러렌(fullerene), 카본 나노튜브(carbon nanotube), 카바이드(carbides), 풀러렌(fullerene) 및 금속 나노선으로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것인,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 변화 감지 섬유.pH change sensing fiber.
  4. 제1항에 있어서,The method of claim 1,
    상기 pH 감응 충진제는, The pH-sensitive filler,
    폴리아닐린(polyaniline), 폴리피롤(polypyrrole), 폴리-N-메틸피롤(poly-N-methylpyrrole), 폴리티오펜(polythiopHene), 폴리(에틸렌디옥시티오펜)[poly(ethylenedioxythiopHene)], 폴리-3-메틸티오펜(poly-3-methylthiopHene), 폴리(3,4-에틸렌디옥시티오펜)[poly(3,4-ethylenedioxythipHene); PEDOT], 폴리(p-페닐렌비닐렌)[poly(ppHenylenevinylene); PPV] 및 폴리퓨란(polyfuran)으로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것인,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 변화 감지 섬유.pH change sensing fiber.
  5. 제1항에 있어서,The method of claim 1,
    상기 금속 전선은, Ag, Au, Ni, Cu, Zn, Fe, Al, Ti, Pt, Hg 및 Pb로 이루어진 군으로부터 선택되는 적어도 어느 하나의 금속을 포함하는 전선이고, 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,
    상기 금속 전선 상에 염화은이 코팅된 것인, Silver chloride is coated on the metal wire,
    pH 변화 감지 섬유.pH change sensing fiber.
  6. 제1항에 있어서,The method of claim 1,
    상기 금속염/고분자 복합체의 금속염은, LiCl, NaCl, NaCN, KCl, KBr, KF, KCN, MgCl2, MgBr2, FeCl2, NiCl2, CuSO4, Cu(Tos)2, CuCl2, CuBr2, ZnCl2, Ag2SO4, IrCl3, H2PtCl6, AuCl3 및 HgCl2로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것이고,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,
    상기 금속염/고분자 복합체의 고분자는, The polymer of the metal salt / polymer complex is,
    폴리디메틸실록산(polydimethylsiloxane; PDMS), 폴리메틸페닐실록산, 폴리메틸비닐실록산, 폴리디페닐실록산 및 폴리(부틸렌-아디페이트-코테레프탈레이트)(poly(butylene-adipate-coterephthalate))로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 것인, selected from the group consisting of polydimethylsiloxane (PDMS), polymethylphenylsiloxane, polymethylvinylsiloxane, polydiphenylsiloxane and poly(butylene-adipate-coterephthalate) which includes at least any one of
    pH 변화 감지 섬유.pH change sensing fiber.
  7. 제1항에 있어서,The method of claim 1,
    상기 작동전극 및 상기 기준전극은 서로 꼬인 구조를 가지는 것인,The working electrode and the reference electrode will have a twisted structure with each other,
    pH 변화 감지 섬유.pH change sensing fiber.
  8. 제1항의 pH 변화 감지 섬유가 직물에 직조된 pH 변화 감지 직물.The pH change sensing fabric in which the pH change sensing fiber of claim 1 is woven into the fabric.
  9. 제8항에 있어서,9. The method of claim 8,
    상기 pH 변화 감지 직물은, The pH change sensing fabric,
    상기 직물에 작동전극 및 기준전극이 서로 크로스바 어레이 구조로 직조된 것인,That the working electrode and the reference electrode are woven into the fabric in a crossbar array structure with each other,
    pH 변화 감지 직물.pH change sensing fabric.
  10. 제1항의 pH 변화 감지 섬유 또는 제8의 pH 변화 감지 직물을 포함하는 pH 변화 감지 센서.A pH change sensor comprising the pH change sensing fabric of claim 1 or the pH change sensing fabric of claim 8 .
PCT/KR2021/006985 2020-10-06 2021-06-04 Ph change sensing fiber, ph change sensing fabric, and ph change sensor comprising same WO2022075549A1 (en)

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