CN107941778A - A kind of sensor and its methods for making and using same for being used to detect body fluid pH - Google Patents

A kind of sensor and its methods for making and using same for being used to detect body fluid pH Download PDF

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Publication number
CN107941778A
CN107941778A CN201710943779.4A CN201710943779A CN107941778A CN 107941778 A CN107941778 A CN 107941778A CN 201710943779 A CN201710943779 A CN 201710943779A CN 107941778 A CN107941778 A CN 107941778A
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China
Prior art keywords
body fluid
sensor
substrate
detect body
metal
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CN201710943779.4A
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周翠萍
董茂龙
何琳
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Southern Hospital Southern Medical University
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Southern Hospital Southern Medical University
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Priority to CN201710943779.4A priority Critical patent/CN107941778A/en
Publication of CN107941778A publication Critical patent/CN107941778A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

Abstract

The invention discloses a kind of sensor and its methods for making and using same for being used to detect body fluid pH.This sensor for being used to detect body fluid pH, including metal Nano structure substrate, metal Nano structure substrate are wrapped with hydrogen ion concentration sensitive material.The preparation method and application process of this sensor for being used to detect body fluid pH are also disclosed that at the same time.The biology sensor based on localised plasmon resonance principle of the invention have the advantages that high throughput, detecting instrument simply, reliable results and cheap, by the way that the material layer of hydrogen ion concentration sensitivity is coated on metal Nano structure, quick detection and monitoring available for human body fluid pH.Sensor of the invention technology of preparing is simple, of low cost and can integrate, suitable for producing in enormous quantities.

Description

A kind of sensor and its methods for making and using same for being used to detect body fluid pH
Technical field
The present invention relates to a kind of sensor and its methods for making and using same for being used to detect body fluid pH.
Background technology
The acid-base value (pH value) of human body fluid can reflect a variety of Biochemical Informations.For example the pH value of local wound microenvironment can pass through shadow Ringing many aspects such as tissue oxygen evolution, revascularization, bacterial virulence, enzymatic activity influences wound healing, by detecting and monitoring pH Value, adjusts the acid-base value of local wound microenvironment, peomotes refractory wounds (wound, burn, pressure sore, diabetes related ulcers) Reparation.For another example, saliva pH can reflect the pathological and physiological condition in oral cavity, low pH and dentine, the burn into mucosal inflammation of enamel Correlation, and the stability and resistance to corrosion of oral cavity titanium prosthesis surface film oxide can be reduced, detection oral pH helps In the early prevention and treatment of mouth disease.In addition, the pH value detection of gastric juice can reflect part gastrointestinal disease state and therapeutic effect, gastric juice PH value detection and monitoring clinically possess more important clinical meaning.
There are electrochemical method and optical means currently for the detection method of body fluid pH.Electrochemical method result is easily subject to The interference of solion, and electrode easily pollutes.Compared to electrochemical method, optical means is more suitable for the detection of pH.Detect saliva The optical means of liquid pH includes fluorescence method and chemoluminescence method., it is necessary to more complicated light path system in fluorescence and chemoluminescence method, And detection environment is required.Compared to fluorescence and chemoluminescence method, the biology biography based on localised plasmon resonance principle Sensor has high throughput, and instrument needed for detection is simple, reliable results, it is cheap the advantages that.
Metal Nano structure has unique light, electricity, magnetic property, suitable for making LSPR (Localized Surface Plasmon Resonance, localized surface plasmons resonance) biological sensing element.In Jie of nanostructured outer cladding sensitivity Electric material can be used for detecting different kinds of molecules, therefore have potential application value in portable medical and field of fast detection.And For nanostructured as LSPR sensing elements, the application for monitoring molecule or ion concentration in the body fluid in addition to blood rarely has report Road.
The content of the invention
It is an object of the invention to provide a kind of sensor and its methods for making and using same for being used to detect body fluid pH.
The technical solution used in the present invention is:
A kind of sensor for being used to detect body fluid pH, including metal Nano structure substrate, metal Nano structure substrate outsourcing It is wrapped with hydrogen ion concentration sensitive material.
Metal Nano structure substrate is wherein one in nano-metal particle substrate, nano metal cone oldered array substrate Kind.
The thickness of hydrogen ion concentration sensitive material is 5nm~20 μm.
Hydrogen ion concentration sensitive material is at least one of polyaniline, polypyrrole layer, polypropylene acid layer.
A kind of preparation method of above-mentioned sensor for being used to detect body fluid pH, is by chemical oxidization method, in metal nano Hydrogen ion concentration sensitive material is deposited in structural substrates.
In preparation method, chemical oxidization method is solution polymerization process or emulsion polymerization.
In preparation method, metal Nano structure substrate is obtained after optical clear substrate is immersed in nano-metal particle solution Arrive, or nano metal cone oldered array is obtained after surfactant solution activation process.
A kind of integrated device for being used to detect body fluid pH, including a kind of above-mentioned sensor, hair for detecting body fluid pH Optical diode light source and film crystal pipe detector.
A kind of method for detecting body fluid pH, is using a kind of above-mentioned integrated device detection body fluid for being used to detect body fluid pH PH change.
Body fluid is the one of which in wound fluid, saliva, gastric juice.
The beneficial effects of the invention are as follows:
Biology sensor of the invention based on localised plasmon resonance principle is with high throughput, detecting instrument is simple, ties The advantages that fruit is reliable and cheap, by the way that the material layer of hydrogen ion concentration sensitivity is coated on metal Nano structure, can use In the quick detection and monitoring of human body fluid (such as wound fluid, saliva, gastric juice) pH.Sensor of the invention technology of preparing Simply, it is of low cost and can integrate, suitable for producing in enormous quantities.
Brief description of the drawings
Fig. 1 is sensor construction schematic diagram made from embodiment 2;
Fig. 2 is the scanning electron microscope (SEM) photograph of the sensor surface of embodiment 2;
Fig. 3 is response diagram of the sensor to pH of embodiment 2.
Embodiment
A kind of sensor for being used to detect body fluid pH, including metal Nano structure substrate, metal Nano structure substrate outsourcing It is wrapped with hydrogen ion concentration sensitive material.
Preferably, metal Nano structure substrate is nano-metal particle substrate, in nano metal cone oldered array substrate One of which;It is further preferred that metal Nano structure substrate is nanogold particle substrate or aluminium nanocone oldered array substrate.
The thickness of hydrogen ion concentration sensitive material is 5nm~20 μm.
Preferably, hydrogen ion concentration sensitive material is at least one in polyaniline, polypyrrole layer, polypropylene acid layer Kind;It is further preferred that hydrogen ion concentration sensitive material is polyaniline.
A kind of preparation method of above-mentioned sensor for being used to detect body fluid pH, is by chemical oxidization method, in metal nano Hydrogen ion concentration sensitive material is deposited in structural substrates.
In preparation method, it is preferred that chemical oxidization method is solution polymerization process or emulsion polymerization.
Further, it is that metal Nano structure substrate is immersed in containing hydrogen when chemical oxidization method is solution polymerization process Reacted in ion concentration sensitive material monomer, initiator and medium solution, the sensor for detecting body fluid pH is made.
Further, when chemical oxidization method is emulsion polymerization, be by metal Nano structure substrate be first immersed in containing In the mixed liquor of hydrogen ion concentration sensitive material monomer and emulsifying agent, initiator for reaction is added, is made for detecting body fluid pH Sensor.
Preferably, it is aniline containing hydrogen ion concentration sensitive material monomer;Medium solution is hydrochloric acid solution;Initiator was Ammonium sulfate;Emulsifying agent is sodium dodecyl sulfate.
In preparation method, it is preferred that metal Nano structure substrate is that optical clear substrate is immersed in nano-metal particle Obtained after solution, or nano metal cone oldered array is obtained after surfactant solution activation process.
Preferably, optical clear substrate is substrate of glass;Nano-metal particle solution is nanogold particle solution;Nanogold It is aluminium nanocone oldered array to belong to cone oldered array;Surfactant is cetyl trimethyl ammonium.
Specifically, metal Nano structure substrate is by manufactured after glass matrix immersion nanogold particle solution, it is described Nanogold particle be by made of the method for citrate reduction gold chloride;Alternatively, metal Nano structure substrate is to pass through Made of after the immersion cetyl trimethyl ammonium solution activation of aluminium nanocone oldered array.
A kind of integrated device for being used to detect body fluid pH, including a kind of above-mentioned sensor, hair for detecting body fluid pH Optical diode light source and film crystal pipe detector.
Further, sensor, LED source and film crystal pipe detector are integrated for detecting body The integrated device of liquid pH.
A kind of method for detecting body fluid pH, is using a kind of above-mentioned integrated device detection body fluid for being used to detect body fluid pH PH change.
Body fluid is the one of which in wound fluid, saliva, gastric juice.
The principle of pH sensings of the present invention is as follows:The material for being wrapped in metallic nanostructured surface has sensitivity to hydrogen ion Property, or have response to the doping level of proton.When the pH value of surrounding environment changes, hydrogen ion sensitive material can be due to Proton doping level is different and the change on electricity structure occurs, and this change will influence the folding on nano structural material surface Rate is penetrated, and then influences the LSPR effects of nanostructured.The influence of this LSPR effects not only shows as LSPR peaks on collection of illustrative plates Red shift or blue shift, and with the change of macroscopic solution colour.And the usually this proton to hydrogen ion sensitive material is mixed Miscellaneous is completely reversibility, therefore the response of the metal Nano structure composite material can also have preferable invertibity and reappearance.
Present disclosure is described in further detail below by way of specific embodiment.
Embodiment 1:
For the sensor of embodiment 1 using aluminium (Al) nanocone structures array as element, polyaniline is sensitive material, specific system Preparation Method is as follows:
Step 1:First by clean Al nano-cone arrays be immersed in cetyl trimethyl ammonium (CTAB solution, In 0.5M), 5min is stood.
Step 2:Then Al nano-cone arrays are taken out, after being cleaned with pure water, is put into aniline (2mM, 1.5mL) and 12 In sodium alkyl sulfate (SDS, 40mM, 0.25mL) mixed solution, 2min is fully vibrated;
Step 3:Secondly, hydrochloric acid solution (the 2mM ammonium persulfates/10mM salt containing ammonium persulfate are added in the solution Acid, 1.5mL), vibration is uniformly mixed solution;
Step 4:Reaction proceeds by after standing.After standing 3~24h, Al nano-cone arrays are taken out from solution, are used The clean array surface of pure water rinsing is that can obtain the Al nano-cone arrays of polyaniline in surface modification.
Step 5:The polyaniline thickness on Al nano-cone arrays surface can be adjusted by controlling the reaction time:During reaction Between it is longer, the thickness of polyaniline is thicker.After 24h, react basic and stop.At this time, repeating above step can further increase The thickness of addition polymerization aniline parcel, the thickness section of polyaniline parcel are advisable with 5nm~20 μm.
Embodiment 2:
For the sensor of embodiment 2 using glass as base material, gold nano grain is element, and polyaniline is sensitive material, its The structure of the visible attached drawing 1 of structure is schematic diagram.In Fig. 1,1- substrate of glass;2- gold nano grains;3- polyanilines.Specific system Preparation Method is as follows:
Step 1:Substrate preparation:Substrate of glass is cleaned, hydrophilicity-imparting treatment.
Step 2:The synthesis of gold nano grain:The water of addition 20mL, which is put into -4 DEG C of refrigerator, in beaker A cools down;Again Separately a beaker B is taken to add ultra-pure water, the sodium citrate solution of 1mL and the chlorauric acid solution of 1mL inward;Weigh the boron of 0.038g Sodium hydride is placed in beaker C, takes the frozen water of 10mL to be added in beaker C from beaker A;Then solvent sodium borohydride solution is taken 1mL is added in beaker B and rocks at once.Beaker B need to be encased with tinfoil does lucifuge processing, when standing 4 is small, can obtain required Seed solution.1.83g CTAB are taken after adding the water of 100mL, to be placed in supersonic cleaning machine in beaker D and accelerate CTAB Dissolving;Solvent CTAB is poured into beaker E, F, G respectively, adds suitable sodium hydroxide solution, Vitamin C inward respectively Acid solution and chlorauric acid solution;Take the seed solution synthesized by 1mL to be added in beaker E and rock rapidly, take 5mL immediately after Solution in E is added in beaker F and rocks rapidly;Take the solution in the beaker F of 2.5mL to be added in beaker G again, then will Stand more than 7h after beaker G sealings, after then adding sodium chloride solution inward, stand 12 it is small when after, gold nano grain will be Beaker bottom deposits.
Step 3:The making of gold nano grain substrate:The nano particle that the step of taking 3mL two synthesizes is centrifuged and is resuspended 2 times Obtain nanogold particle solution;The substrate of glass for the hydrophilicity-imparting treatment that step 1 is obtained is soaked in 24 in gold nano grain solution Hour, obtain gold nano grain substrate.
Step 4:Polyaniline is wrapped up in gold nano grain substrate surface:(aniline monomer concentration is configuration mixed liquor 2.0mM, ammonium persulfate concentrations 2mM, surfactant SDS concentration are 40mM), pH is adjusted in 2.0, by step with concentrated hydrochloric acid Three obtained nanogold particle substrates are soaked in the mixing liquid of beaker;6 it is small when after, solution in beaker is changed into blackish green Color, takes out slide rinse repeatedly, removes the polyaniline and ammonium persulfate of its surface excess;Then it is being baked to, drying is completed Nanogold-polyaniline composite particles sensor is just obtained afterwards.
Attached drawing 2 is the scanning electron microscope (SEM) photograph of the sensor surface of embodiment 2.As it is clear from fig. 2 that polyaniline covering is uniform, and Gold nano structure has been wrapped up, effectively forms sensitive layer.Attached drawing 3 is response diagram of the sensor to pH of embodiment 2.Can from Fig. 3 See, the sensor of embodiment 2 has good response effect in the different sections that different pH are 3~5;In pH 4.0, photoresponse is strong Degree keeps basicly stable.
Sensor made from embodiment 2 and LED source, film crystal pipe detector are integrated for examining Survey the integrated device of body fluid pH.This integrated device is placed in the facing in oral cavity, detects the signal strength and letter of thin film transistor (TFT) Number Strength Changes can detection mouth intracavitary saliva pH changes.

Claims (10)

  1. A kind of 1. sensor for being used to detect body fluid pH, it is characterised in that:Including metal Nano structure substrate, metal Nano structure Substrate is wrapped with hydrogen ion concentration sensitive material.
  2. A kind of 2. sensor for being used to detect body fluid pH according to claim 1, it is characterised in that:Metal Nano structure base Bottom is nano-metal particle substrate, the one of which in nano metal cone oldered array substrate.
  3. A kind of 3. sensor for being used to detect body fluid pH according to claim 1, it is characterised in that:Hydrogen ion concentration is sensitive The thickness of material layer is 5nm~20 μm.
  4. A kind of 4. sensor for being used to detect body fluid pH according to claim 3, it is characterised in that:Hydrogen ion concentration is sensitive Material layer is at least one of polyaniline, polypyrrole layer, polypropylene acid layer.
  5. 5. a kind of preparation method for the sensor for being used to detect body fluid pH of Claims 1 to 4 any one of them, its feature exist In:By chemical oxidization method, hydrogen ion concentration sensitive material is deposited in metal Nano structure substrate.
  6. A kind of 6. preparation method of sensor for being used to detect body fluid pH according to claim 5, it is characterised in that:Chemistry Oxidizing process is solution polymerization process or emulsion polymerization.
  7. A kind of 7. preparation method of sensor for being used to detect body fluid pH according to claim 5, it is characterised in that:Metal Nanostructured substrate obtains after optical clear substrate is immersed in nano-metal particle solution, or nano metal is bored What oldered array obtained after surfactant solution activation process.
  8. A kind of 8. integrated device for being used to detect body fluid pH, it is characterised in that:Passed including Claims 1 to 4 any one of them Sensor, LED source and film crystal pipe detector.
  9. A kind of 9. method for detecting body fluid pH, it is characterised in that:The pH of integrated device detection body fluid described in usage right requirement 8 Change.
  10. A kind of 10. method for detecting body fluid pH according to claim 9, it is characterised in that:Body fluid is wound fluid, saliva One of which in liquid, gastric juice.
CN201710943779.4A 2017-10-11 2017-10-11 A kind of sensor and its methods for making and using same for being used to detect body fluid pH Pending CN107941778A (en)

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CN109700600A (en) * 2018-12-18 2019-05-03 中国人民解放军第四军医大学 PH sensor, sensing dressing and manufacture, building method comprising the sensor
CN110186875A (en) * 2019-05-21 2019-08-30 天津大学 Surface plasmon resonance optical-fiber type pH value measurement method and sensor
CN110373708A (en) * 2019-07-31 2019-10-25 东南大学 Adjustable concentration realizes that the nanometer pinpoint of needle point cone angle control prepares platform and method

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Publication number Priority date Publication date Assignee Title
CN109700600A (en) * 2018-12-18 2019-05-03 中国人民解放军第四军医大学 PH sensor, sensing dressing and manufacture, building method comprising the sensor
CN110186875A (en) * 2019-05-21 2019-08-30 天津大学 Surface plasmon resonance optical-fiber type pH value measurement method and sensor
CN110373708A (en) * 2019-07-31 2019-10-25 东南大学 Adjustable concentration realizes that the nanometer pinpoint of needle point cone angle control prepares platform and method
CN110373708B (en) * 2019-07-31 2021-04-30 东南大学 Nano needle tip preparation platform and method for adjusting concentration to realize needle tip cone angle control

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