CN104764725B - Monitor the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen - Google Patents

Monitor the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen Download PDF

Info

Publication number
CN104764725B
CN104764725B CN201510171727.0A CN201510171727A CN104764725B CN 104764725 B CN104764725 B CN 104764725B CN 201510171727 A CN201510171727 A CN 201510171727A CN 104764725 B CN104764725 B CN 104764725B
Authority
CN
China
Prior art keywords
oxygen
particulate
optical fiber
sensitivity
partial pressure
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.)
Active
Application number
CN201510171727.0A
Other languages
Chinese (zh)
Other versions
CN104764725A (en
Inventor
曹汇敏
杨云
王四祥
谢勤岚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South Central Minzu University
Original Assignee
South Central University for Nationalities
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South Central University for Nationalities filed Critical South Central University for Nationalities
Priority to CN201510171727.0A priority Critical patent/CN104764725B/en
Publication of CN104764725A publication Critical patent/CN104764725A/en
Application granted granted Critical
Publication of CN104764725B publication Critical patent/CN104764725B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The present invention provides a kind of two-parameter fluorescent optical fiber sensor probe of the single-point for monitoring pH value and partial pressure of oxygen, including optical fiber probe, the polyurethane hydrogel layer being fixed on optical fiber probe and the scattered pH sensitivities particulate and oxygen sensitivity particulate being embedded in polyurethane hydrogel layer, it is characterised in that:The pH sensitivities particulate is prepared by the way that HPTS to be covalently fixed on to amino modified p HEMA, and the oxygen sensitivity particulate is by solvent chloroform by Ru (dpp)3 2+Organic modified silicate is embedded in be prepared.The present invention can solve that the problems such as Resonance energy transfer causes cross jamming, more indicator that the photodissociation that can cause indicator and signal drift coexists occurs in traditional sensors between more indicator.

Description

Monitor the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen
Technical field
The present invention relates to a kind of two-parameter fluorescent optical fiber sensor probe of the single-point for monitoring pH value and partial pressure of oxygen.
Background technology
In medical clinic applicationses, the partial pressure of oxygen (pO of blood2) and acid-base value (pH value) be assess patient's pathologic, physiologic shape Two important Testing index of state.In the critical patient cares such as shock, respiratory failure, brain damage and great anesthesia surgery, need Will be by frequently determining the pO of blood or tissue2The oxygen equilibrium of supply and demand of patient and acid-base balance state are evaluated with pH value.
At present, it is clinical more using conventional blood gas analyzer, by intermittent arterial blood drawing, in vitro change is carried out to blood sample Credit analysis draws pO2With many reference amounts information such as pH value.Several big shortcomings be present in conventional blood gas analysis:The vim and vigour snapshot of interruption can not be accurate Really reflect continuous physiological event;Blood gas analysis, possible delay treatment are only generally carried out after adverse reaction occurs;It is non real-time In vitro analysis exist blood sample change or pollution risk;Repeatedly blood sampling may also result in iatrogenic anemia.
Undoubtedly, in situ, real-time, noninvasive, many reference amounts can be carried out to blood, tissue even individual cells to detect, Through as the active demand in biomedical clinical and life science.In order to measure many reference amounts letter in organism simultaneously Breath, people successively propose various biomedical multi-parameter sensing solutions, such as laboratory on chemical microarray, piece (Lab on a chip), micro-total analysis system (μ-TAS), bio-microelectromechanical system (Bio MEMS) etc..They are all minute yardstick The in-situ study of lower many reference amounts provides feasible means, but there is needing, consumption measured object, reliability are poor, manufacture mostly The problems such as Platform Requirements are high, monitoring system complexity.Therefore the multifunctional sensing probe (joining sensitive membrane more) of microminiature is that restriction is more Parametrical sense device further develops and moved towards the bottleneck of clinical practice.
With optical fiber, the development of photoelectron technology, and the advantages that Stability of Optical Fiber Sensor height, strong antijamming capability, Increasing researcher starts to realize the measurement of partial pressure of oxygen in blood, pH value etc. using fluorescent fiber technique, successively carries The measuring method of partial pressure of oxygen and pH value based on optical fiber is gone out.Fudan University reported is fixed on biology by the complex compound of metal Ru In the fabulous phosphocholine ester polymer of compatibility, it is directly anchored to optical fiber connector and makes blood oxygen transducer, this sensor is not Only high sensitivity, stability are good and have good bio-compatibility.
Fluorescence optical fiber joins sensor more and is broadly divided into two classes according to principle:Array many reference amounts fluorescent optical fiber sensor and single-point More ginseng fluorescent optical fiber sensors.The U.S. once reported the fluorescent optical sensor on array multi-parameter, but its probe is general bigger; Need multiple light sources and light processing equipment, the cost of making is higher;" the blood vessel wall effect " showed in clinic causes accurately Property is not high so that it is difficult to put goods on the market.In addition, existing single-point joins fluorescent optical fiber sensor more has spectrum in the design process It is overlapped, interfered between indicator, photodissociation and signal drift so that design fibre-optical probe is sufficiently complex, and accuracy is not It is high.
The content of the invention
The present invention provides a kind of two-parameter fluorescent optical fiber sensor probe of the single-point for monitoring pH value and partial pressure of oxygen, can solve Occur that Resonance energy transfer causes cross jamming, more indicator coexist can cause indicator in traditional sensors between more indicator Photodissociation and the problems such as signal drift.
A kind of two-parameter fluorescent optical fiber sensor probe of single-point for monitoring pH value and partial pressure of oxygen, including optical fiber probe, fixation Polyurethane hydrogel layer and the scattered pH sensitivities particulate being embedded in polyurethane hydrogel layer and oxygen on optical fiber probe is sensitive Particulate, it is characterised in that:The pH sensitivities particulate is prepared by the way that HPTS to be covalently fixed on to amino modified p-HEMA, institute Oxygen sensitivity particulate is stated by solvent chloroform by Ru (dpp)3 2+Organic modified silicate is embedded in be prepared.
Further, amino modified p-HEMA is prepared by following steps:Take a certain amount of toluene and ethanolamine salt Hydrochlorate, according to toluene:The mass ratio 4~6 of ethanolamine hydrochloric salt:1 is added in three-neck flask, stir and be heated to 100 DEG C~ After 150 DEG C, appropriate methacrylic chloride is slowly added dropwise dropwise, after being added dropwise, continues stirring 2~5 hours, is cooled to 10 DEG C To -20 DEG C, after solid precipitation, filtering, the toluene or diisopropyl ether of the same dosage of filter residue, decompression drying, you can obtain Amino modified p-HEMA.
Further, pH sensitivities particulate is prepared by following steps:Take the p-HEMA that 200mg~500mg is amino modified It is dissolved in 100mL~500mL distilled water, then takes 4mg~10mg HPTS to add during mixing is dissolved in, after stirring ten minutes, The EDC for adding 5mg~100mg is stirred for 2~5 hours, the buffering that the buffer solution for the use of distilled water, pH being then 4, pH are 9 Liquid, alcohol wash until colourless successively, on the sheet glass that sediment has been positioned ready for, dry, with sand paper by sheet glass Polymer is polished, and is pulverized, you can obtain pH sensitivity particulates.
Further, organic modified silicate is prepared by following steps:Configure 0.1mol/L hydrochloric acid, take 25mL~ 100mL ethanol is put into round-bottomed flask, then takes the trimethoxy-benzene base silane of same dosage to be dissolved into ethanol, and mixing is equal It is even, then the 0.1mol/L configured hydrochloric acid is dripped in round-bottomed flask, round-bottomed flask is put into 65 DEG C~100 DEG C of water-bath In, continue 2.5~5 hours, according to trimethoxy-benzene base silane and trimethyl methoxy silane molar ratio 10~20:1 adds Trimethyl methoxy silane, after reaction continues 1~3 hour again, cooling, after round-bottomed flask thoroughly cooling, add 2/3 round bottom and burn The distilled water of bottle capacity prevents the further progress of reaction, and round-bottomed flask is stood into 8~12 hours, grease is fully precipitated Remove aqueous phase after forming latex, latex is placed in 150 DEG C~200 DEG C of drying box and dries 5-8 hour, crushed into powder shape It can obtain organic modified silicate.
Further, oxygen sensitivity particulate is prepared by following steps:Take 5mg~100mg Ru (dpp)3Cl2With Na- TMS is in separatory funnel, wherein Ru (dpp)3Cl2It is less than 1 with Na-TMS mol ratio:2, add 50mL~200mL distilled water It is well mixed, the chloroform extraction of 5/4 times of distilled water volume is then added, obtains Ru (dpp)3(TMS)2Chloroformic solution, will distill The organic modified silicate that 4~10 times of water volume is put into the Ru (dpp) equipped with 20mL~100mL3(TMS)2Chloroformic solution, make It sufficiently disperses, and stirs, and then with ethanol wash, centrifugal mixer, on the sheet glass that sediment has been positioned ready for, dries in the air It is dry, the polymer on sheet glass is polished with sand paper, pulverizes, obtains oxygen sensitivity particulate.
Further, pH sensitivities particulate and the scattered embedded polyurethane hydrogel layer of oxygen sensitivity particulate concretely comprise the following steps:Take 5mg ~100mg polyurethane hydrogel and appropriate alcoholic solution are well mixed, and alcohol and water volume ratio are 9 in alcoholic solution:1, Alcoholic solution and polyurethane hydrogel are according to mass ratio 19:1 is configured to polyurethane hydrogel solution, takes 10mg~100mg oxygen Sensitive particulate and 14mg~150mg pH sensitivity particulates are uniformly distributed in 300mg~500mg polyurethane hydrogel solution, stirring Overnight.
The present invention has the following advantages that compared with prior art:
1) indicator has selectivity, and its sensitivity is controllable, and pH sensitivities particulate only passes through proton, and oxygen is quick Sense particulate only passes through oxygen, can adjust sensitivity and selectivity by changing the ratio of two sensitive particulates.
2) cross sensitivity caused by fluorescent quenching is reduced by the selective penetrated property of particulate, solved in traditional sensors Resonance energy transfer occurs between more indicator causes cross jamming, more indicator that the photodissociation that can cause indicator and signal drift coexists The problems such as shifting, because the use that required die-away time has obvious difference and polymer is quenched in two fluorescence indicators, this By the cross-sensitivity caused by more indicator, and respectively sensitive particulate is made in two indicator by the present invention, can be prevented more Indicator spatially caused photodissociation.
3) outstanding photostability, the pH that caused singlet oxygen will not be in photodissociation pH sensitivity particulates in oxygen sensitivity particulate refer to Show agent;By in the good polymer substrate of oxygen sensitivity particulate and pH sensitivities particulate insertion bio-compatibility, initiative can overcome intersection Double ginseng fluorescence senses probe of interference, important tool is provided for the monitoring and diagnosis and treatment of major disease in biomedical clinical.
Brief description of the drawings
Fig. 1 is the structural representation of the two-parameter fluorescent optical fiber sensor probe of single-point of present invention monitoring pH value and partial pressure of oxygen Figure;
Fig. 2 is Ru (dpp)3(Cl)2(three (4,7- biphenyl -1,10- phenanthroline) ruthenous chlorides) is dissolved in chloroformic solution, The fluorescence spectra for exciting to obtain using 470nm light;
Fig. 3 is Ru (dpp)3(TMS)2(three (4,7- biphenyl -1,10- phenanthrolines) two (3- trimethyl silicon substrate third sulphurs of -1- Acid) change ruthenium) embedding after be dissolved in chloroformic solution, the fluorescence spectra for exciting to obtain using 470nm light;
Fig. 4 is that HPTS is dissolved under solid conditions, and obtained spectrogram is excited with 470nm light;
Fig. 5 be HPTS and amino modified p-HEMA it is covalently fixed after, excited obtained spectrogram with 470nm;
Fig. 6 be HPTS and amino modified p-HEMA it is covalently fixed after, in the case where 550nm absorbs, to exciting light Absorbing state spectrogram.
In figure:1-optical fiber probe, 2-polyurethane hydrogel layer, 3-pH sensitivity particulates, 4-oxygen sensitivity particulate.
Embodiment
Below in conjunction with the accompanying drawing in the present invention, the technical scheme in the present invention is clearly and completely described.
The structure that Fig. 1 show the two-parameter fluorescent optical fiber sensor probe of single-point of present invention monitoring pH value and partial pressure of oxygen is shown It is intended to, the two-parameter fluorescent optical fiber sensor probe of single-point of the monitoring pH value and partial pressure of oxygen includes optical fiber probe 1, is fixed on light Polyurethane hydrogel layer 2 on fine probe 1 and the pH sensitivities particulate 3 and oxygen sensitivity particulate being embedded in polyurethane hydrogel layer 2 4, wherein pH sensitivities particulate 3 is amino modified by the way that HPTS (8- hydroxyl pyrenes -1,3,6- trisulfonic acids trisodium salt) is covalently fixed on P-HEMA (amino modified poly hydroxyethyl methylacrylate) is prepared, and to avoid the spilling of indicator, oxygen sensitivity particulate 4 leads to Solvent chloroform is crossed by Ru (dpp)3 2+Organic modified silicate is embedded in be prepared, it is preferably selective and steady to obtain Qualitative, the application of organic modified silicate preferably resolves crackle and hydrophilic problem, while also remains organically-modified The advantages of silicate is film-made.
(1) amino modified p-HEMA synthesis
Take a certain amount of toluene and ethanolamine hydrochloric salt, the mass ratio of toluene and ethanolamine hydrochloric salt is 4~6:1, add Into three-neck flask, after stirring and being heated to 100 DEG C~150 DEG C, appropriate methacrylic chloride is slowly added dropwise dropwise.Drip Bi Hou, continue stirring 2~5 hours, be cooled to 10 DEG C Dao -20 DEG C.After solid precipitation, filtering, the toluene of the same dosage of filter residue Or diisopropyl ether.Decompression drying, obtain amino modified p-HEMA.
(2) synthesis of pH sensitivities particulate 3
Take amino modified p-HEMA (the amino modified Poly-HEMAs prepared in 200mg~500mg (1) Ester) and HPTS (8- hydroxyl pyrenes -1,3,6- trisulfonic acids trisodium salt) be dissolved in 100mL~500mL distilled water, wherein amino modified Poly hydroxyethyl methylacrylate and 8- hydroxyl pyrene -1,3,6- trisulfonic acid trisodium salts mass ratio 50:1 to 70:Between 1, stir After mixing about ten minutes, 5mg-100mg EDC (1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides) is added, then is stirred Mix about 2~5 hours.Then distilled water is used, pH is 4 buffer solutions, and pH is that 9 buffer solutions and alcohol wash until colourless successively. On the sheet glass that sediment has been positioned ready for, dry.The polymer on sheet glass is polished with sand paper, pulverized, you can obtain PH sensitivity particulates.
Amino modified p-HEMA synthesis based on this method is relatively easy to be realized and relatively cheap, then is passed through Covalently fixed mode, pH indicator HPTS is covalently fixed to the synthesis that pH sensitivity particulates are realized in p-HEMA.Fig. 4 and Fig. 5 It is that the launch wavelengths of both fluorescence spectras excited to pH indicator before and after covalently fixed with 470nm light exists At 542nm.Fig. 6 is then the maximum excitation for confirming the pH indicator after covalent fixation still in 470nm.Drawn by detection, After covalent fix, the excitation peak and absworption peak of pH indicator are not moved.
(3) synthesis of organic modified silicate
According to trimethoxy-benzene base silane and trimethyl methoxy silane molar ratio 10~20:1 prepares organic modified silicas acid Salt.Shown by table 1 and compared by experiment, the inventors discovered that when trimethoxy-benzene base silane and trimethyl methoxy silane mole Ratio is 18:When 1, the organic modified silicate performance obtained by this method is best, there is preferable optical stability, and And the big I of particulate controls according to the actual effect of the present invention.
The different trimethoxy-benzene base silanes of table 1 obtain the performance of oxygen sensitivity particulate with trimethyl methoxy silane molar ratio
0.1mol/L hydrochloric acid is configured, takes 25mL~100mL ethanol to be put into round-bottomed flask, then take the three of same dosage Methoxybenzene base silane is dissolved into ethanol, is well mixed, then the 0.1mol/L configured hydrochloric acid is dripped in round-bottomed flask (an acid environment is provided).Round-bottomed flask is put into 65 DEG C~100 DEG C of water-bath.Continue 2.5~5 hours, press According to trimethoxy-benzene base silane and trimethyl methoxy silane molar ratio 18:1 adds trimethyl methoxy silane, and reaction continues 1 again After~3 hours, cooling.After round-bottomed flask thoroughly cooling, the distilled water for adding 2/3 round-bottomed flask capacity prevents entering for reaction One step is carried out.By round-bottomed flask stand 8~12 hours, make grease fully precipitate to form latex after remove aqueous phase, by latex It is placed in 150 DEG C~200 DEG C of drying box and dries 5~8 hours., will in order to obtain the more preferable organic modified silicate of performance The solid that above-mentioned steps obtain is placed in 200 DEG C~280 DEG C of drying box, and with the air in vacuum pump depletion drying box, 12~15 hours are dried, then crushed into powder shape can obtain organic modified silicate.
(4) synthesis of oxygen sensitivity particulate 4
Take 5mg-100mg Ru (dpp)3Cl2(three (4,7- biphenyl -1,10- phenanthrolines) ruthenous chlorides) and Na-TMS (3- trimethyl silicon substrate -1- propane sulfonic acid sodium salt) is in separatory funnel, wherein three (4,7- biphenyl -1,10- phenanthroline) dichlorides The mol ratio of ruthenium and 3- trimethyl silicon substrate -1- propane sulfonic acid sodium salts is less than 1:2, the distilled water for adding 50mL~200mL is well mixed. Then appropriate chloroform (the 5/4 of distilled water) is added, extracts, obtains Ru (dpp)3(TMS)2Chloroformic solution.Will appropriate (distillation 4-10 times of water volume) organic modified silicate be put into the Ru (dpp) equipped with 20mL~100mL3(TMS)2Chloroformic solution, It is sufficiently disperseed, stir, then with ethanol wash, centrifugal mixer.On the sheet glass that sediment has been positioned ready for, Dry.The polymer on sheet glass is polished with sand paper, pulverizes, obtains oxygen sensitivity particulate.
Oxygen sensitivity particulate based on the synthesis of this method is also substantially accelerated to the response speed of oxygen, and does not interfere with Ru (dpp)3(TMS)2Fluorescent quenching.As shown in Figures 2 and 3, it is to be directed to Ru (dpp)3(Cl)2With use organic modified silicate Oxygen sensitivity particulate after embedding, carries out exciting the fluorescence spectra made on XRF with 470nm blue light.
(5) pH sensitivities particulate 3 and the scattered embedded polyurethane hydrogel layer 2 of oxygen sensitivity particulate 4
Detailed process be take 5mg~100mg polyurethane hydrogel and appropriate alcoholic solution (alcohol and water volume ratio are 9:1) it is well mixed, alcoholic solution and polyurethane hydrogel are according to mass ratio 19:1 is configured to polyurethane hydrogel solution.Take 10mg~100mg Ru (dpp)3 2+/ ormosil particulates (i.e. oxygen sensitivity particulate 4) and 14mg~150mg HPTS/p-HEMA are micro- Grain (i.e. pH sensitivities particulate 3) is uniformly distributed in 300mg~500mg polyurethane hydrogel solution, is stirred overnight.By 1000nm light Fine probe tip is immersed into above-mentioned mixed solution, is then placed at room temperature in atmospheric environment and is dried 24h, that is, completes this The making of the two-parameter fluorescent optical fiber sensor probe of the described single-point of invention.
The principle of the present invention is to utilize two kinds of different indicator (HPTS, Ru (dpp)3 2+) there is identical absworption peak, it is different Fluorescence lifetime, pH indicator HPTS fluorescence lifetime is ns levels, oxygen indicator Ru (dpp)3 2+Fluorescence lifetime be us levels, profit With LED light source in the case where double frequency timesharing excites, pH value determination and partial pressure of oxygen simultaneously are realized using low frequency phase modulation method.Specifically, this hair Bright two indicator using fluorescence lifetime significant difference:PH indicator HPT (peak value excitation/emission ripple 468/542nm) is ns levels Short life indicator, oxygen indicator Ru (dpp)3 2+(peak value excitation/emission wavelength 468/608nm) is us level long-life indicator, Under exciting light Sine Modulated, the transmitting light with two indicator of different fluorescence lifetimes is also same frequency sine-wave.In kHz scopes Under low modulation frequencies, the amplitude of short-life indicator transmitting light changes with tested pH value, and phase keeps constant, and the long-life The amplitude and phase of indicator transmitting light are with tested pO2Change, if measuring total phase under two different modulating frequencies simultaneously Move, it is possible to parse the two tested parameters.The application field of the present invention can be generalized to cell training from biomedical clinical The fields such as foster, biofermentation, marine ecology, monitoring water quality, food hygiene.
It is as shown in table 2 the actual effect checking of the present invention, actual verification method of the invention is that test pH is respectively 7.53rd, the result of the gas mixing gas test of different partial is passed through in 6.86,4 solution.The composition of mixed gas is oxygen The mixed gas of gas and nitrogen, actual test are to each lead into the mixed gas that partial pressure of oxygen is 5kPa and 15kPa.In LED drive In the case of dynamic frequency is respectively 30KHz and 60KHz, the actual phase shift and amplitude of drive signal are obtained by digital lock-in amplifier Change, then pass through corresponding data processing and obtain the pH of solution and the actual measured value of partial pressure of oxygen.
The actual verification result of the mixed gas of different partial (kPa) is passed through in the different pH solution of table 2
From table 2 can, can measure pH and partial pressure of oxygen simultaneously using inventive sensor probe, and error is smaller, And the partial pressure of oxygen measured in different pH solution is relatively stable, and is surveyed in the pH solution for being passed through different partial The pH obtained does not also have greatly changed with the change of partial pressure of oxygen.So can be drawn from measurement data, supervise at the same time Not obvious measurement interference between two parameter while surveying two parameter.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in, all should It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.

Claims (4)

1. a kind of two-parameter fluorescent optical fiber sensor probe of single-point for monitoring pH value and partial pressure of oxygen, including optical fiber probe, it is fixed on Polyurethane hydrogel layer and the scattered pH sensitivities particulate being embedded in polyurethane hydrogel layer and oxygen sensitivity on optical fiber probe is micro- Grain, it is characterised in that:The pH sensitivities particulate is prepared by the way that HPTS to be covalently fixed on to amino modified p-HEMA, described Oxygen sensitivity particulate is by solvent chloroform by Ru (dpp)3 2+Organic modified silicate is embedded in be prepared;
The organic modified silicate is prepared by following steps:0.1mol/L hydrochloric acid is configured, takes 25mL~100mL second Alcohol is put into round-bottomed flask, then takes the trimethoxy-benzene base silane of same dosage to be dissolved into ethanol, is well mixed, then will configuration Good 0.1mol/L hydrochloric acid is dripped in round-bottomed flask, round-bottomed flask is put into 65 DEG C~100 DEG C of water-bath, is continued 2.5 ~5 hours, according to trimethoxy-benzene base silane and trimethyl methoxy silane molar ratio 10~20:1 adds trimethyl methoxy Silane, after reaction continues 1~3 hour again, cooling, after round-bottomed flask thoroughly cooling, add the steaming of 2/3 round-bottomed flask capacity Distilled water prevents the further progress of reaction, round-bottomed flask is stood into 8~12 hours, after grease is fully precipitated and is formed latex Remove aqueous phase, latex is placed in 150 DEG C~200 DEG C of drying box and dries 5~8 hours, crushed into powder shape is i.e. available Organic modified silicate;
The pH sensitivities particulate and the scattered embedded polyurethane hydrogel layer of oxygen sensitivity particulate concretely comprise the following steps:Take 5mg-100mg's Polyurethane hydrogel and appropriate alcoholic solution are well mixed, and alcohol and water volume ratio are 9 in alcoholic solution:1, alcoholic solution and Polyurethane hydrogel is according to mass ratio 19:1 is configured to polyurethane hydrogel solution, take 10mg~100mg oxygen sensitivity particulate and 14mg~150mg pH sensitivity particulates are uniformly distributed in 300mg~500mg polyurethane hydrogel solution, are stirred overnight.
2. the two-parameter fluorescent optical fiber sensor probe of the single-point of monitoring pH value and partial pressure of oxygen as claimed in claim 1, its feature It is:Amino modified p-HEMA is prepared by following steps:A certain amount of toluene and ethanolamine hydrochloric salt are taken, according to first Benzene:The mass ratio 4~6 of ethanolamine hydrochloric salt:1 is added in three-neck flask, after stirring and being heated to 100 DEG C~150 DEG C, slowly Appropriate methacrylic chloride is added dropwise dropwise, after being added dropwise, continues stirring 2~5 hours, is cooled to 10 DEG C Dao -20 DEG C, treats solid After body separates out, filtering, the toluene or diisopropyl ether of the same dosage of filter residue, decompression drying, you can obtain amino modified p- HEMA。
3. the two-parameter fluorescent optical fiber sensor probe of the single-point of monitoring pH value and partial pressure of oxygen as claimed in claim 1 or 2, it is special Sign is:PH sensitivity particulates are prepared by following steps:The p-HEMA for taking 200mg~500mg amino modified be dissolved in 100mL~ In 500mL distilled water, then take 4mg~10mg HPTS to add during mixing is dissolved in, after stirring ten minutes, add 5mg~ 100mg EDC is stirred for 2~5 hours, buffer solution that the buffer solution for the use of distilled water, pH being then 4, pH are 9, alcohol according to Secondary washing on the sheet glass for being positioned ready for sediment, is dried, is beaten the polymer on sheet glass with sand paper until colourless Mill, pulverizes, you can obtain pH sensitivity particulates.
4. the two-parameter fluorescent optical fiber sensor probe of the single-point of monitoring pH value and partial pressure of oxygen as claimed in claim 1, its feature It is:Oxygen sensitivity particulate is prepared by following steps:Take 5mg~100mg Ru (dpp)3Cl2With Na-TMS in separatory funnel In, wherein Ru (dpp)3Cl2It is less than 1 with Na-TMS mol ratio:2, the distilled water for adding 50mL~200mL is well mixed, then The chloroform extraction of 5/4 times of distilled water volume is added, obtains Ru (dpp)3(TMS)2Chloroformic solution, by 4~10 times of distilled water volume Organic modified silicate be put into the Ru (dpp) equipped with 20mL~100mL3(TMS)2Chloroformic solution, it is sufficiently disperseed, Stir, then with ethanol wash, centrifugal mixer, on the sheet glass that sediment has been positioned ready for, dry, with sand paper by glass Polymer polishing on glass piece, pulverizes, obtains oxygen sensitivity particulate.
CN201510171727.0A 2015-04-13 2015-04-13 Monitor the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen Active CN104764725B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510171727.0A CN104764725B (en) 2015-04-13 2015-04-13 Monitor the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510171727.0A CN104764725B (en) 2015-04-13 2015-04-13 Monitor the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen

Publications (2)

Publication Number Publication Date
CN104764725A CN104764725A (en) 2015-07-08
CN104764725B true CN104764725B (en) 2017-11-24

Family

ID=53646689

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510171727.0A Active CN104764725B (en) 2015-04-13 2015-04-13 Monitor the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen

Country Status (1)

Country Link
CN (1) CN104764725B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3380827B1 (en) * 2015-11-23 2023-11-29 Revvity Health Sciences, Inc. Hollow polymer fiber optic system for single analyte and multiplexed analyte detection
CN105784664A (en) * 2016-05-10 2016-07-20 南京工业大学 Hydrogel microsphere type fluorescence sensor, preparation method and application
CN108572165B (en) * 2018-06-19 2019-09-24 南京大学 A kind of pH plate optrode fluorescence sense film, preparation method and application
CN110124097A (en) * 2019-05-31 2019-08-16 盐城工学院 A kind of preparation method of bacterial cellulose slow-release dressing

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1947658A (en) * 2005-10-14 2007-04-18 复旦大学附属中山医院 In-vivo real-time photo-sensitive blood pH value sensor and its making method
CN101713735A (en) * 2008-10-07 2010-05-26 中国科学院大连化学物理研究所 Oxygen-sensitive fluorescent membrane and preparation method thereof
FR2955592B1 (en) * 2010-01-27 2016-04-15 Millipore Corp CULTURE MEDIUM FOR THE DETECTION OF MICROORGANISMS BY FLUORESCENCE ALLIING A FLUOROGENEOUS SUBSTRATE AND A PH-SENSITIVE FLUOROPHORE
CN202005753U (en) * 2011-03-25 2011-10-12 复旦大学附属中山医院 Fluorescent optical fiber sensor capable of monitoring dissolved oxygen partial pressure and pH (potential of hydrogen) value in blood

Also Published As

Publication number Publication date
CN104764725A (en) 2015-07-08

Similar Documents

Publication Publication Date Title
CN104764725B (en) Monitor the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen
JP4808777B2 (en) Non-volatile analyte concentration measurement method
Frankaer et al. Optical chemical sensor using intensity ratiometric fluorescence signals for fast and reliable pH determination
Abugo et al. Fluorescence properties of rhodamine 800 in whole blood and plasma
US20100222657A1 (en) Method for glucose monitoring using fluorescence quenching
US7943390B2 (en) Supported molecular biofluid viscosity sensors for in vitro and in vivo use
JPH09503866A (en) Light emitting quenching sensor
CN101865853B (en) Stabilized beta-hydroxybutyric acid detection test paper and preparation method thereof
CN101438145A (en) Optical probe
CN103998619B (en) Method for determining analyte concentration
CN105555192B (en) Adjusting to chemical optics sensor for percutaneous application
CN105928914A (en) Hydrogen sulfide detection sensor, preparation method thereof, quantitative detection method of hydrogen sulfide, and qualitative detection method of hydrogen sulfide in cells
CN105044087B (en) Urine examination device for fast detecting and method
US9518928B2 (en) Optode for determining chemical parameters
JP6074070B2 (en) Correction of osmotic pressure fluctuations in chemical-optical sensor spots
CA2892053A1 (en) Multi-layer device for selectively determining magnesium ion
EP1820027A1 (en) Cholesterol assay
CN112730367B (en) Method and device for determining alkaline phosphatase by multi-signal spectrum sensing platform based on portable intelligent terminal
ES2971975T3 (en) Sensor with self-reference
CN105392425B (en) Application of the barrier contact medium in the chemistry-chemistry-optical sensor percutaneously used
CN104597257A (en) Rapid myoglobin detection method and corresponding detection kit
JPH11183475A (en) Humor inspection system
CN213030631U (en) Standard template for fluorescence calibration
RU2547893C1 (en) Method of detecting gas-phase acetone
CN111961466B (en) Carbon quantum dot fluorescent probe for detecting heparin

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant