CN111839532A - 一种基于导电水凝胶的柔性表皮电化学生物传感器 - Google Patents
一种基于导电水凝胶的柔性表皮电化学生物传感器 Download PDFInfo
- Publication number
- CN111839532A CN111839532A CN202010675959.0A CN202010675959A CN111839532A CN 111839532 A CN111839532 A CN 111839532A CN 202010675959 A CN202010675959 A CN 202010675959A CN 111839532 A CN111839532 A CN 111839532A
- Authority
- CN
- China
- Prior art keywords
- conductive hydrogel
- electrode
- film substrate
- electrochemical biosensor
- working electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 52
- 210000002615 epidermis Anatomy 0.000 title description 3
- 230000005518 electrochemistry Effects 0.000 title description 2
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims abstract description 5
- 238000005266 casting Methods 0.000 claims abstract description 4
- 229920002678 cellulose Polymers 0.000 claims abstract description 4
- 239000001913 cellulose Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 3
- 210000001124 body fluid Anatomy 0.000 claims description 11
- 239000010839 body fluid Substances 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 238000007641 inkjet printing Methods 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 5
- 108010015776 Glucose oxidase Proteins 0.000 claims description 4
- 239000004366 Glucose oxidase Substances 0.000 claims description 4
- 235000019420 glucose oxidase Nutrition 0.000 claims description 4
- 229940116332 glucose oxidase Drugs 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000011370 conductive nanoparticle Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229920001046 Nanocellulose Polymers 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 6
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 3
- 229960003237 betaine Drugs 0.000 claims 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 description 8
- 210000003491 skin Anatomy 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 201000010099 disease Diseases 0.000 description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- -1 polydimethylsiloxane Polymers 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 210000003722 extracellular fluid Anatomy 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 2
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 2
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 206010012601 diabetes mellitus Diseases 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229940116269 uric acid Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 231100000517 death Toxicity 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011337 individualized treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
- A61B5/14507—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue specially adapted for measuring characteristics of body fluids other than blood
- A61B5/1451—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue specially adapted for measuring characteristics of body fluids other than blood for interstitial fluid
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
- A61B5/14507—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue specially adapted for measuring characteristics of body fluids other than blood
- A61B5/14517—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue specially adapted for measuring characteristics of body fluids other than blood for sweat
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
- A61B5/14532—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue for measuring glucose, e.g. by tissue impedance measurement
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
- A61B5/14546—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue for measuring analytes not otherwise provided for, e.g. ions, cytochromes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
- A61B5/1468—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using chemical or electrochemical methods, e.g. by polarographic means
- A61B5/1477—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using chemical or electrochemical methods, e.g. by polarographic means non-invasive
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
- A61B5/6801—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be attached to or worn on the body surface
- A61B5/683—Means for maintaining contact with the body
- A61B5/6832—Means for maintaining contact with the body using adhesives
- A61B5/6833—Adhesive patches
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
- A61B2562/12—Manufacturing methods specially adapted for producing sensors for in-vivo measurements
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
- A61B2562/16—Details of sensor housings or probes; Details of structural supports for sensors
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
- A61B2562/16—Details of sensor housings or probes; Details of structural supports for sensors
- A61B2562/164—Details of sensor housings or probes; Details of structural supports for sensors the sensor is mounted in or on a conformable substrate or carrier
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Animal Behavior & Ethology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Medical Informatics (AREA)
- Veterinary Medicine (AREA)
- Surgery (AREA)
- Biophysics (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
本发明公开一种基于导电水凝胶的柔性表皮电化学生物传感器，包括导电水凝胶薄膜基底层、设置在所述基底层上的参比电极、对电极、用于测量生物分子的工作电极和与外部设备连接的信号线。导电水凝胶薄膜基底层的制备方法如下：在纳米纤维素溶液中加入两性离子聚合物单体，再加入热引发剂和交联剂，搅拌至少20分钟；将制备好的上述水凝胶电解质室温下静置过夜，做消泡处理；然后将静置后的溶液倒入玻璃模具中流延成膜，并在加热板上放置，最终制备得到具有良好导电性能的水凝胶薄膜基底。本发明提高目标分子检测性能及穿戴舒适度的要求。
Description
技术领域
本发明涉及电化学传感器领域，具体涉及一种基于导电水凝胶的柔性表皮电化学生物传感器。
背景技术
随着全世界疾病人数的不断增加以及疾病诊断不及时导致的死亡人数的不断增多,实现对疾病的早期快速灵敏检测受到人们越来越多的关注。如人类常见的糖尿病，人体血糖异常会直接导致糖尿病的产生。如果能对人体生理活性物质实现快速、高灵敏度、高选择性、即时定量检测，为拟定更加合理﹑个体化的治疗方案，提供有价值的临床依据，从而更好地指导疾病的治疗具有非常重要的意义。
现已有人提出将柔性表皮电化学生物传感器用于人类疾病的检测。该技术是通过采用电化学传感器检测人体体液(如汗液、组织液等)中目标分子(如葡萄糖分子、乳酸分子等)浓度的方法来间接得到血液中目标分子的浓度。该技术能够在最大限度地减少创伤的基础上，实现人体不同分子浓度的动态、连续监测，技术原理相对简单，具有可实现性强、使用方便、测量速度快等特点。
然而目前大多数柔性表皮电化学生物传感器都是以固体聚合物为基底，如聚二甲基硅氧烷、聚对苯二甲酸乙二醇酯和聚酰亚胺等，但是皮肤时刻在进行新陈代谢，检测过程中体液会不断的更新累积，此类聚合物具有结构致密的特点，不能够有效吸收储存或排除检测完成的体液。若长期佩戴以上述聚合物为基底的传感器，体液的累积会对目标分子的检测灵敏度产生严重干扰；甚至会引发皮肤炎症，影响穿戴舒适性。
发明内容
为了使柔性表皮电化学生物传感器能够满足提高目标分子检测性能及穿戴舒适度的要求，我们提出以具有良好储水性能及生物相容性的水凝胶作为柔性表皮电化学传感器的基底，并采用掺杂的方法对水凝胶进行改进，制备具有良好导电性能的导电水凝胶，然后利用喷墨打印技术以导电水凝胶为基底制备柔性表皮电化学生物传感器。
本发明提出一种基于导电水凝胶的柔性表皮电化学生物传感器，用于实现对体液(如汗液、组织液)中目标分子(如葡萄糖分子、乳酸分子、尿酸分子等)的高灵敏连续检测。
本发明所采用的技术方案是：一种基于导电水凝胶的柔性表皮电化学生物传感器，包括导电水凝胶薄膜基底层、设置在所述基底层上的参比电极、对电极、用于测量生物分子的工作电极和与外部设备连接的信号线。
所述的电化学生物传感器用于检测体液中的生物分子。
所述导电水凝胶薄膜基底层的制备方法：
在纳米纤维素中加入两性离子聚合物单体，
再加入热引发剂和交联剂，搅拌至少20分钟；
将制备好的上述水凝胶电解质室温下静置过夜，做消泡处理；
然后将静置后的溶液倒入玻璃模具中流延成膜，并在加热板上放置，最终制备得到具有良好导电性能的水凝胶薄膜基底。
所述两性离子包括如羧酸甜菜碱、磺酸甜菜碱、硫酸酯甜菜碱等。
所述热引发剂和交联剂的质量比为4：1。
本发明利用喷墨打印的方式在导电水凝胶薄膜基上打印一层金属银，然后利用三氯化铁溶液对银电极进行氯化处理，得到参比电极和对电极；然后采用喷墨打印的方式在导电水凝胶薄膜基底上打印一层金属作为工作电极的基底电极，然后再在金属层上用喷墨打印的方式修饰一层导电纳米颗粒，然后固定葡萄糖氧化酶构成工作电极，将导电水凝胶薄膜基底从玻璃模具上剥离即完成整个电化学葡萄糖传感器的制作。
本发明具有如下优点：
1.导电水凝胶薄膜基底具有较高的离子导电率，有效提高了电子迁移率，提高了对体液中目标生物分子的检测性能。
2.导电水凝胶薄膜基底的有效储水功能，能够有效的缓解体液累积对目标分子检测带来的干扰。
3.导电水凝胶薄膜基底中两性离子基团缔合的极性和带电基团增强电极与凝胶电解质之间的界面粘合性。
4.导电水凝胶薄膜基底良好的柔性、机械性能、生物相容性能够与皮肤共形贴合，且长时间贴合在皮肤表面不易对人体皮肤产生刺激。
5.导电水凝胶的制备过程中，以一种聚合物的骨架引发两性离子聚合物的聚合，步骤简单、成本低廉且易于控制。
附图说明
图1是本发明基于导电水凝胶修饰的柔性表皮电化学生物传感器；
附图标记：
1：参比电极
2：工作电极
3：对电极
4：信号线
5：导电水凝胶薄膜基底层
具体实施方式
下面结合实施例和附图对本发明的基于导电水凝胶修饰的柔性表皮电化学生物传感器做出详细说明。
如图1所示，采用本发明方法所制备的基于导电水凝胶的柔性表皮电化学生物传感器，整个传感器制作在与人体皮肤表皮共形贴合的导电水凝胶薄膜基底层5上，用于连续监测人体血糖浓度。传感器由参比电极1、工作电极2和对电极3组成，所述的参比电极1、工作电极2和对电极3分别通过信号线4连接外部设备。
导电水凝胶膜的详细制备过程：按[2-甲基丙烯酰氧基)乙基]二硫-(3-磺丙基)与纳米纤维素质量比为1：4的比例，将[2-甲基丙烯酰氧基)乙基]二硫-(3-磺丙基)加入1.7％的纳米纤维素溶液中并不断搅拌，将过硫酸钾(或过硫酸铵)和的N,N-亚甲基二丙烯酰胺按4：1的质量比依次加入上述混合溶液中，将该混合溶液至少搅拌20分钟。将制备好的上述混合溶液室温下静置过夜，做消泡处理。然后将静置后的溶液倒入玻璃模具中流延成膜，并在60℃的加热板上放置2-3小时，最终制备得到具有良好导电性能的水凝胶薄膜基底。两性离子还可以包括羧酸甜菜碱、硫酸酯甜菜碱。
所述的导电水凝胶薄膜基底作为柔性表皮电化学生物传感器的基底，具有能促进离子迁移的离子通道网络、良好的柔韧性和优异的保水性能及生物相容性。将其作为柔性表皮电化学生物传感器的基底能够有效缓解检测过程中体液的累积对检测灵敏度产生的干扰；而且其良好的生物相容性不会对人体皮肤产生刺激，且水凝胶能够很好的贴合皮肤，这能够保持柔性表皮电化学生物传感器再佩戴过程中的舒适度；此外，其促进离子迁移的离子通道网络结构能够有效加快电化学检测过程中的离子迁移效率，增强导电性能。
利用喷墨打印的方式在导电水凝胶薄膜基5上打印一层金属银，然后利用三氯化铁溶液对银电极进行氯化处理，得到参比电极1和对电极3；然后采用喷墨打印的方式在导电水凝胶薄膜基底上打印一层金属(如金)作为工作电极2的基底电极，然后再在金属层上用喷墨打印的方式修饰一层导电纳米颗粒(如石墨烯、铂纳米颗粒等)用于加快电子转移效率，然后固定葡萄糖氧化酶构成工作电极3，将导电水凝胶薄膜基底从玻璃模具上剥离即完成整个电化学葡萄糖传感器的制作。
所述的参比电极1、工作电极2和对电极3共同构成对体液(如汗液、细胞间质液等)中目标分子浓度(葡萄糖分子、乳酸分子、尿酸分子等)进行检测的电化学传感器，可在外部设备的控制下实现对目标分子浓度的原位、实时采集。
将传感器与皮肤粘合好后，即可进行葡萄糖浓度的检测：这里的检测体系是传感器中的参比电极1、工作电极2和对电极3共同形成的电化学传感器，如图1所示，在工作电极2施加-0.6V—+0.6V(相对于参比电极)的电压范围，并使得工作电极2与对电极3之间形成测量回路，葡萄糖氧化酶特异性催化葡萄糖的分解，在恒电势下电化学反应中电子的转移速率即电化学反应中的电流与待测液中葡萄糖的浓度成正比，通过检测该电流(即对电极3和工作电极2之间的电流)的大小就可以获得待测液中葡萄糖的浓度。
本发明公开和揭示的所有组合可以通过借鉴本文公开内容产生，尽管本发明的组合已通过详细实施过程进行了描述，但是本领域技术人员明显能在不脱离本发明内容、精神和范围内对本发明所述的装置进行拼接或改动，或增减某些部件，更具体地说，所有相类似的替换和改动对本领域技术人员来说是显而易见的，他们都被视为包括在本发明精神、范围和内容之中。
Claims (6)
1.一种基于导电水凝胶的柔性表皮电化学生物传感器，其特征在于，包括导电水凝胶薄膜基底层、设置在所述基底层上的参比电极、对电极、用于测量生物分子的工作电极和与外部设备连接的信号线；
导电水凝胶薄膜基底层的制备方法如下：
在纳米纤维素溶液中加入两性离子聚合物单体，
再加入热引发剂和交联剂，搅拌至少20分钟；
将制备好的上述水凝胶电解质室温下静置过夜，做消泡处理；
然后将静置后的溶液倒入玻璃模具中流延成膜，并在加热板上放置，最终制备得到具有良好导电性能的水凝胶薄膜基底。
2.根据权利要求1所述的基于导电水凝胶的柔性表皮电化学生物传感器，其特征在于，所述的电化学生物传感器用于检测体液中的生物分子。
3.根据权利要求1所述的基于导电水凝胶的柔性表皮电化学生物传感器，其特征在于，两性离子包括但不限于羧酸甜菜碱、磺酸甜菜碱、硫酸酯甜菜碱。
4.根据权利要求1所述的基于导电水凝胶的柔性表皮电化学生物传感器，其特征在于，热引发剂和交联剂的质量比为4：1。
5.根据权利要求1所述的基于导电水凝胶的柔性表皮电化学生物传感器，其特征在于，纳米纤维素溶液质量分数为1.7％。
6.根据权利要求1所述的基于导电水凝胶的柔性表皮电化学生物传感器，其特征在于，利用喷墨打印的方式在导电水凝胶薄膜基上打印一层金属银，然后利用三氯化铁溶液对银电极进行氯化处理，得到参比电极和对电极；然后采用喷墨打印的方式在导电水凝胶薄膜基底上打印一层金属作为工作电极的基底电极，然后再在金属层上用喷墨打印的方式修饰一层导电纳米颗粒，然后固定葡萄糖氧化酶构成工作电极，将导电水凝胶薄膜基底从玻璃模具上剥离即完成整个电化学葡萄糖传感器的制作。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010675959.0A CN111839532A (zh) | 2020-07-14 | 2020-07-14 | 一种基于导电水凝胶的柔性表皮电化学生物传感器 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010675959.0A CN111839532A (zh) | 2020-07-14 | 2020-07-14 | 一种基于导电水凝胶的柔性表皮电化学生物传感器 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111839532A true CN111839532A (zh) | 2020-10-30 |
Family
ID=72983866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010675959.0A Pending CN111839532A (zh) | 2020-07-14 | 2020-07-14 | 一种基于导电水凝胶的柔性表皮电化学生物传感器 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111839532A (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717405A (zh) * | 2021-09-24 | 2021-11-30 | 天津中电新能源研究院有限公司 | 一种柔性导电水凝胶及其制备方法和应用 |
| CN114441611A (zh) * | 2021-12-22 | 2022-05-06 | 天津大学 | 基于有机场效应晶体管的宽动态测量范围葡萄糖传感器 |
| WO2022106981A1 (en) * | 2020-11-18 | 2022-05-27 | Camlin Italy S.R.L. | A patch for application to human or animal organ and a process for manufacturing thereof |
| CN115931992A (zh) * | 2022-11-02 | 2023-04-07 | 南京农业大学 | 一种可用于肉类新鲜度检测的柔性电子材料的制备方法及其应用 |
Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101664562A (zh) * | 2009-09-30 | 2010-03-10 | 都本立 | 创伤修复水凝胶材料及制备方法 |
| CN102764447A (zh) * | 2012-07-27 | 2012-11-07 | 武汉人福医疗用品有限公司 | 水凝胶敷料及其制备工艺 |
| CN103131232A (zh) * | 2013-03-27 | 2013-06-05 | 北京大学 | 高性能水性石墨烯导电涂料及其制备方法 |
| CN103619129A (zh) * | 2013-11-25 | 2014-03-05 | 深圳大学 | 一种喷墨打印铜导电线路的方法 |
| CN104007150A (zh) * | 2013-12-04 | 2014-08-27 | 西南大学 | 基于导电聚合物的全印刷生物及环境传感器及其制备方法 |
| CN105445339A (zh) * | 2014-07-31 | 2016-03-30 | 天津大学 | 一种柔性差分式阵列电化学葡萄糖传感器及使用方法 |
| CN105513833A (zh) * | 2015-12-24 | 2016-04-20 | 宁波南车新能源科技有限公司 | 一种锂离子电容器电极的涂覆系统及其涂覆方法 |
| US20160141065A1 (en) * | 2013-03-28 | 2016-05-19 | Tohoku University | Porous substrate electrode body and method for producing same |
| CN107202823A (zh) * | 2017-06-20 | 2017-09-26 | 龚雨 | 一种喷墨印刷制备微电极阵列传感器的方法及其应用 |
| CN107898467A (zh) * | 2017-10-21 | 2018-04-13 | 天津大学 | 用于葡萄糖连续检测的柔性表皮微流体采集系统 |
| CN109012618A (zh) * | 2018-09-12 | 2018-12-18 | 宝泰隆新材料股份有限公司北京分公司 | 一种氧化石墨烯/海藻酸钠凝胶球的制备方法和应用 |
| CN109044327A (zh) * | 2018-08-08 | 2018-12-21 | 厦门大学 | 一种刺入力度可控的微针干式电极 |
| CN109148897A (zh) * | 2017-06-16 | 2019-01-04 | 通用汽车环球科技运作有限责任公司 | 用于防止离聚物渗透的基底热控制 |
| CN109215687A (zh) * | 2018-08-21 | 2019-01-15 | 北京印刷学院 | 用于光信息存储的柔性透明存储器及制备方法 |
| US20190127490A1 (en) * | 2016-05-19 | 2019-05-02 | President And Fellows Of Harvard College | Methods of making gels and films using curli nanofibers |
| CN109771820A (zh) * | 2018-01-08 | 2019-05-21 | 成都柔电云科科技有限公司 | 一种导电水凝胶电刺激贴片及其制备方法与应用 |
| CN110128596A (zh) * | 2019-07-12 | 2019-08-16 | 苏州宏久航空防热材料科技有限公司 | 一种高透明可拉伸自愈合离子导电纳米复合水凝胶及其制备方法 |
| CN110604561A (zh) * | 2019-06-19 | 2019-12-24 | 北京大学 | 一种水凝胶基电子学器件及其制备方法与应用 |
| US20200002560A1 (en) * | 2018-06-29 | 2020-01-02 | Chung-Ping Lai | Conductive ink for use in manufacturing radio frequency identification (rfid) tag antenna and method for manufacturing rfid tag antenna |
| CN110776652A (zh) * | 2019-10-23 | 2020-02-11 | 重庆医科大学 | 石墨烯基导电水凝胶和其制备方法及在柔性可穿戴式传感器上的应用 |
| CN110970232A (zh) * | 2019-11-25 | 2020-04-07 | 中山大学 | 以水凝胶为基底的可拉伸微型电子器件及制备方法 |
| US20200107758A1 (en) * | 2018-10-09 | 2020-04-09 | General Electric Company | Wearable sweat sensing systems and methods thereof |
-
2020
- 2020-07-14 CN CN202010675959.0A patent/CN111839532A/zh active Pending
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101664562A (zh) * | 2009-09-30 | 2010-03-10 | 都本立 | 创伤修复水凝胶材料及制备方法 |
| CN102764447A (zh) * | 2012-07-27 | 2012-11-07 | 武汉人福医疗用品有限公司 | 水凝胶敷料及其制备工艺 |
| CN103131232A (zh) * | 2013-03-27 | 2013-06-05 | 北京大学 | 高性能水性石墨烯导电涂料及其制备方法 |
| US20160141065A1 (en) * | 2013-03-28 | 2016-05-19 | Tohoku University | Porous substrate electrode body and method for producing same |
| CN103619129A (zh) * | 2013-11-25 | 2014-03-05 | 深圳大学 | 一种喷墨打印铜导电线路的方法 |
| CN104007150A (zh) * | 2013-12-04 | 2014-08-27 | 西南大学 | 基于导电聚合物的全印刷生物及环境传感器及其制备方法 |
| CN105445339A (zh) * | 2014-07-31 | 2016-03-30 | 天津大学 | 一种柔性差分式阵列电化学葡萄糖传感器及使用方法 |
| CN105513833A (zh) * | 2015-12-24 | 2016-04-20 | 宁波南车新能源科技有限公司 | 一种锂离子电容器电极的涂覆系统及其涂覆方法 |
| US20190127490A1 (en) * | 2016-05-19 | 2019-05-02 | President And Fellows Of Harvard College | Methods of making gels and films using curli nanofibers |
| CN109148897A (zh) * | 2017-06-16 | 2019-01-04 | 通用汽车环球科技运作有限责任公司 | 用于防止离聚物渗透的基底热控制 |
| CN107202823A (zh) * | 2017-06-20 | 2017-09-26 | 龚雨 | 一种喷墨印刷制备微电极阵列传感器的方法及其应用 |
| CN107898467A (zh) * | 2017-10-21 | 2018-04-13 | 天津大学 | 用于葡萄糖连续检测的柔性表皮微流体采集系统 |
| CN109771820A (zh) * | 2018-01-08 | 2019-05-21 | 成都柔电云科科技有限公司 | 一种导电水凝胶电刺激贴片及其制备方法与应用 |
| US20200002560A1 (en) * | 2018-06-29 | 2020-01-02 | Chung-Ping Lai | Conductive ink for use in manufacturing radio frequency identification (rfid) tag antenna and method for manufacturing rfid tag antenna |
| CN109044327A (zh) * | 2018-08-08 | 2018-12-21 | 厦门大学 | 一种刺入力度可控的微针干式电极 |
| CN109215687A (zh) * | 2018-08-21 | 2019-01-15 | 北京印刷学院 | 用于光信息存储的柔性透明存储器及制备方法 |
| CN109012618A (zh) * | 2018-09-12 | 2018-12-18 | 宝泰隆新材料股份有限公司北京分公司 | 一种氧化石墨烯/海藻酸钠凝胶球的制备方法和应用 |
| US20200107758A1 (en) * | 2018-10-09 | 2020-04-09 | General Electric Company | Wearable sweat sensing systems and methods thereof |
| CN110604561A (zh) * | 2019-06-19 | 2019-12-24 | 北京大学 | 一种水凝胶基电子学器件及其制备方法与应用 |
| CN110128596A (zh) * | 2019-07-12 | 2019-08-16 | 苏州宏久航空防热材料科技有限公司 | 一种高透明可拉伸自愈合离子导电纳米复合水凝胶及其制备方法 |
| CN110776652A (zh) * | 2019-10-23 | 2020-02-11 | 重庆医科大学 | 石墨烯基导电水凝胶和其制备方法及在柔性可穿戴式传感器上的应用 |
| CN110970232A (zh) * | 2019-11-25 | 2020-04-07 | 中山大学 | 以水凝胶为基底的可拉伸微型电子器件及制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| FUNIAN MO, ZE CHEN, GUOJIN LIANG, DONGHONG WANG, YUWEI ZHAO, HONGFEI LI, BINBIN DONG, CHUNYI ZHI: "Zwitterionic Sulfobetaine Hydrogel Electrolyte Building Separated Positive/Negative Ion Migration Channels for Aqueous Zn-MnO2 Batteries with Superior Rate Capabilities", 《ADVANCED ENERGY MATERIALS 》, pages 1 - 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022106981A1 (en) * | 2020-11-18 | 2022-05-27 | Camlin Italy S.R.L. | A patch for application to human or animal organ and a process for manufacturing thereof |
| CN113717405A (zh) * | 2021-09-24 | 2021-11-30 | 天津中电新能源研究院有限公司 | 一种柔性导电水凝胶及其制备方法和应用 |
| CN113717405B (zh) * | 2021-09-24 | 2024-05-03 | 天津中电新能源研究院有限公司 | 一种柔性导电水凝胶及其制备方法和应用 |
| CN114441611A (zh) * | 2021-12-22 | 2022-05-06 | 天津大学 | 基于有机场效应晶体管的宽动态测量范围葡萄糖传感器 |
| CN114441611B (zh) * | 2021-12-22 | 2024-03-26 | 天津大学 | 基于有机场效应晶体管的宽动态测量范围葡萄糖传感器 |
| CN115931992A (zh) * | 2022-11-02 | 2023-04-07 | 南京农业大学 | 一种可用于肉类新鲜度检测的柔性电子材料的制备方法及其应用 |
| CN115931992B (zh) * | 2022-11-02 | 2023-12-26 | 南京农业大学 | 一种可用于肉类新鲜度检测的柔性电子材料的制备方法及其应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111839532A (zh) | 一种基于导电水凝胶的柔性表皮电化学生物传感器 | |
| Chinnadayyala et al. | Nonenzymatic determination of glucose at near neutral pH values based on the use of nafion and platinum black coated microneedle electrode array | |
| Li et al. | Rational design and applications of conducting polymer hydrogels as electrochemical biosensors | |
| US5954685A (en) | Electrochemical sensor with dual purpose electrode | |
| CN108828043A (zh) | 一种柔性汗液传感器及其制备方法和应用 | |
| Xu et al. | A wearable sensor based on multifunctional conductive hydrogel for simultaneous accurate pH and tyrosine monitoring in sweat | |
| CN104914150B (zh) | 一种基于石墨烯/聚苯胺复合膜的pH检测电极 | |
| Aerathupalathu Janardhanan et al. | Sensitive detection of sweat cortisol using an organic electrochemical transistor featuring nanostructured poly (3, 4-ethylenedioxythiophene) derivatives in the channel layer | |
| KR102282133B1 (ko) | 플렉서블 pH 센서 및 이의 제조 방법 | |
| CN111655147A (zh) | 生物传感器探针用保护膜材料 | |
| US11359300B1 (en) | Electrochemical method for enzyme immobilization on biosensor electrodes | |
| US20220257181A1 (en) | Minimally invasive continuous analyte monitoring for closed-loop treatment applications | |
| CN111855778B (zh) | 基于两性离子水凝胶多孔酶膜修饰的电化学生物传感器 | |
| CN110604581A (zh) | 一种提高葡萄糖传感器灵敏度的方法 | |
| KR20180006835A (ko) | 바이오 센서 및 그의 제작 방법 | |
| Zhu et al. | Effect of interstitial fluid pH on transdermal glucose extraction by reverse iontophoresis | |
| Zhao et al. | Wearable electrochemical sensors for the detection of organic metabolites and drugs in sweat | |
| JP4366791B2 (ja) | ドーパミンおよびアスコルビン酸を含む被検試料に含まれるドーパミンの濃度を測定するために用いられる修飾電極 | |
| CN111867469A (zh) | 生物传感器探针用保护膜材料 | |
| WO2021163964A1 (zh) | 导电水凝胶的制备方法及其细胞阻抗传感检测方法 | |
| CN210990322U (zh) | 高灵敏度的可穿戴无创葡萄糖传感器 | |
| Yoon et al. | A Flexible Electrochemical-Physiological Epidermal Hybrid Patch for Chronic Disease Management | |
| WO2020117170A1 (en) | Glucose biosensor based on polyphosphonoundecyl acrylate-co-polyvinylimidazole-co-polyvinylferrocene-co-polyglycidyl methacrylate tetra block copolymer | |
| Meng | Tailoring Conducting Polymer Interface for Sensing and Biosensing | |
| CN112515681A (zh) | 离子导电水凝胶电极的制备方法及应用该电极的可穿戴心电传感器 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |