CN104764725A - Single-point double-parameter fluorescence optical fiber sensor probe for monitoring pH value and oxygen partial pressure - Google Patents
Single-point double-parameter fluorescence optical fiber sensor probe for monitoring pH value and oxygen partial pressure Download PDFInfo
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Abstract
The invention provides a single-point double-parameter fluorescence optical fiber sensor probe for monitoring a pH value and oxygen partial pressure. The probe comprises an optical fiber probe, a polyurethane hydrogel layer fixed on the optical fiber probe, and pH-sensitive particles and oxygen-sensitive particles dispersed and embedded into the polyurethane hydrogel layer, and is characterized in that the pH-sensitive particles are prepared by covalently fixing HPTS on the amido modified p-HEMA; and the oxygen-sensitive particles are prepared by embedding Ru(dpp)32+ on organically modified silicate by virtue of solvent trichloromethane. According to the probe disclosed by the invention, the problems that cross interference is caused by resonance energy transfer among multiple indicators, photolysis and signal drift of the indicators can be caused by co-existence of the multiple indicators and the like in the traditional sensor can be solved.
Description
Technical field
The present invention relates to a kind of two-parameter fluorescent optical fiber sensor probe of single-point of monitoring pH value and partial pressure of oxygen.
Background technology
In medical clinic applications, the partial pressure of oxygen (pO of blood
2) and potential of hydrogen (pH value) be two important Testing index of evaluating patient pathological and physiological condition.In the CCNs such as shock, respiratory failure, brain damage and great anesthesia surgery, need the pO by frequently measuring blood or tissue
2the oxygen equilibrium of supply and demand and the acid base equilibrium state of patient is evaluated with pH value.
At present, the conventional blood gas analyzer of clinical many employings, by intermittent arterial blood drawing, carries out in vitro chemical analysis to blood sample and draws pO
2with many reference amounts information such as pH value.There is several large shortcoming in conventional blood gas analysis: the vim and vigour snapshot of interruption cannot reflect continuous print physiological event exactly; Usually only in the laggard row blood gas analysis of generation bad reaction, possible delay treatment; There is the risk that blood sample changes or pollutes in non real-time ex vivo analyses; Repeatedly take a blood sample and also may cause iatrogenic anemia.
Undoubtedly, can blood, tissue or even individual cells be carried out original position, be detected in real time, without wound, many reference amounts, become the active demand in biomedical clinical and life science.In order to measure the many reference amounts information in biosome simultaneously, people successively propose various biomedical multi-parameter sensing solution, as laboratory on chemical microarray, sheet (Lab ona chip), micro-total analysis system (μ-TAS), bio-microelectromechanical system (Bio MEMS) etc.They are all that under microscale, the in-situ study of many reference amounts provides feasible means, but mostly there is problems such as needing consumption measured object, reliability is poor, manufacturing platform requirement is high, monitoring system is complicated.Therefore hypomegetic multifunctional sensing probe (joining sensitive membrane) is the bottleneck that restriction multi-parameter sensor further developed and moved towards clinical practice more.
Along with the development of optical fiber, photoelectron technology, and the advantage such as Stability of Optical Fiber Sensor is high, antijamming capability is strong, increasing researchist starts to adopt fluorescent fiber technique to realize the measurement of partial pressure of oxygen, pH value etc. in blood, successively proposes the measuring method of partial pressure of oxygen based on optical fiber and pH value.Fudan University reported and was fixed in the fabulous phosphocholine ester polymer of bio-compatibility by the complex compound of metal Ru, directly be fixed on optical fiber connector and make blood oxygen transducer, this sensor not only highly sensitive, good stability but also there is good bio-compatibility.
Fluorescence optical fiber many ginsengs sensor is mainly divided into two classes according to principle: array many reference amounts fluorescent optical fiber sensor and single-point many ginsengs fluorescent optical fiber sensor.The U.S. once reported the fluorescent optical sensor about array multiparameter, but its probe is general larger; Need multiple light source and light treatment facility, the cost compare of making is high; Cause accuracy not high in " the vascular wall effect " of clinical middle performance, make to be difficult to put goods on the market.In addition, it is overlapped in the design process to there is spectrum in existing single-point many ginsengs fluorescent optical fiber sensor, mutually disturbs, photodissociation and signal drift between indicator, and make design fibre-optical probe very complicated, accuracy is not high.
Summary of the invention
The invention provides the two-parameter fluorescent optical fiber sensor probe of a kind of single-point of monitoring pH value and partial pressure of oxygen, the problems such as Resonance energy transfer causes cross jamming, many indicator coexist can cause indicator photodissociation and signal drift occur between many indicator can be solved in traditional sensors.
A kind of two-parameter fluorescent optical fiber sensor probe of single-point of monitoring pH value and partial pressure of oxygen, comprise optical fiber probe, be fixed on polyurethane hydrogel layer on optical fiber probe and dispersion and be embedded in the responsive particulate of pH in polyurethane hydrogel layer and the responsive particulate of oxygen, it is characterized in that: the responsive particulate of described pH is prepared from by HPTS covalency is fixed on amino modified p-HEMA, the responsive particulate of described oxygen passes through solvent methenyl choloride by Ru (dpp)
3 2+be embedded in organic modified silicate to be prepared from.
Further, amino modified p-HEMA is prepared from by following steps: get a certain amount of toluene and ethanolamine hydrochloric salt, according to toluene: the mass ratio 4 ~ 6:1 of ethanolamine hydrochloric salt joins in three-neck flask, to stir and after being heated to 100 DEG C ~ 150 DEG C, slowly dropwise drip appropriate methacrylic chloride, after dropwising, continue stirring 2 ~ 5 hours, be cooled to 10 DEG C to-20 DEG C, after solid is separated out, filter, the filter residue toluene of same dosage or diisopropyl ether, decompression drying, can obtain amino modified p-HEMA.
Further, the responsive particulate of pH is prepared from by following steps: get the amino modified p-HEMA of 200mg ~ 500mg and be dissolved in the distilled water of 100mL ~ 500mL, then the HPTS getting 4mg ~ 10mg adds during mixing is dissolved in, stir after ten minutes, the EDC adding 5mg ~ 100mg stirs 2 ~ 5 hours again, then use distilled water, pH be 4 damping fluid, pH be 9 damping fluid, alcohol wash until colourless successively, sediment is placed on ready glass sheet, dry, with sand paper by the polymkeric substance polishing on glass sheet, pulverize, the responsive particulate of pH can be obtained.
Further, organic modified silicate is prepared from by following steps: the hydrochloric acid of configuration 0.1mol/L, the ethanol getting 25mL ~ 100mL is put in round-bottomed flask, the trimethoxy-benzene base silane getting same dosage is again dissolved in ethanol, mix, again the hydrochloric acid of the 0.1mol/L configured is dripped in round-bottomed flask, round-bottomed flask is put into the water-bath of 65 DEG C ~ 100 DEG C, continue 2.5 ~ 5 hours, trimethyl methoxy silane is added according to trimethoxy-benzene base silane and trimethyl methoxy silane molar ratio 10 ~ 20:1, reaction continues after 1 ~ 3 hour again, cooling, after round-bottomed flask thoroughly cools, the distilled water adding 2/3 round-bottomed flask capacity stops carrying out further of reaction, round-bottomed flask is left standstill 8 ~ 12 hours, aqueous phase is removed after making grease fully precipitate formation latex, latex is placed on dry 5-8 in the drying box of 150 DEG C ~ 200 DEG C individual hour, crushed into powder shape can obtain organic modified silicate.
Further, the responsive particulate of oxygen is prepared from by following steps: the Ru (dpp) getting 5mg ~ 100mg
3cl
2with Na-TMS in separating funnel, wherein Ru (dpp)
3cl
2be less than 1:2 with the mol ratio of Na-TMS, the distilled water adding 50mL ~ 200mL mixes, and then adds the chloroform extraction of distilled water volume 5/4 times, obtains Ru (dpp)
3(TMS)
2chloroformic solution, the organic modified silicate of distilled water volume 4 ~ 10 times is put into the Ru (dpp) that 20mL ~ 100mL is housed
3(TMS)
2chloroformic solution, make it disperse fully, stir, then use ethanol wash, centrifugal mixer, sediment is placed on ready glass sheet, dries, with sand paper by the polymkeric substance polishing on glass sheet, pulverize, obtain the responsive particulate of oxygen.
Further, the responsive particulate of pH and the responsive microparticulate of oxygen embed polyurethane hydrogel layer concrete steps and are: polyurethane hydrogel and the appropriate alcoholic solution of getting 5mg ~ 100mg mix, in alcoholic solution, alcohol and water volume ratio are 9:1, alcoholic solution and polyurethane hydrogel are configured to polyurethane hydrogel solution according to mass ratio 19:1, the responsive particulate homogenous of pH of the responsive particulate of oxygen and 14mg ~ 150mg of getting 10mg ~ 100mg is distributed in 300mg ~ 500mg polyurethane hydrogel solution, and stirring is spent the night.
The present invention compared with prior art tool has the following advantages:
1) indicator has selectivity, and its sensitivity can control, and the responsive particulate of pH is only through proton, and the responsive particulate of oxygen, only through oxygen, can regulate sensitivity and selectivity by the ratio changing two responsive particulates.
2) cross sensitivity caused by fluorescent quenching is decreased by the selective penetrated property of particulate, solve in traditional sensors and the problem such as photodissociation and signal drift that Resonance energy transfer causes cross jamming, many indicator coexist can cause indicator occurs between many indicator, due to the use that there is obvious difference and polymkeric substance die-away time needed for two fluorescence indicator cancellation, this is by the cross-sensitivity caused by many indicator, and two indicator are made responsive particulate by the present invention respectively, the photodissociation that many indicator spatially cause can be prevented.
3) outstanding light stability, the singlet oxygen produced in the responsive particulate of oxygen can not pH indicator in the responsive particulate of photodissociation pH; Embed in the good polymer substrate of bio-compatibility by responsive for oxygen particulate and the responsive particulate of pH, initiative can overcome two ginseng fluorescence senses probes of cross jamming, for the monitoring of major disease in biomedical clinical and diagnosis and treatment provide important tool.
Accompanying drawing explanation
Fig. 1 is the structural representation that the present invention monitors the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen;
Fig. 2 is Ru (dpp)
3(Cl)
2(three (4,7-biphenyl-1,10-phenanthroline) ruthenous chloride) is dissolved in chloroformic solution, adopts the fluorescence spectrum figure that the optical excitation of 470nm obtains;
Fig. 3 is Ru (dpp)
3(TMS)
2be dissolved in chloroformic solution after (three (4,7-biphenyl-1,10-phenanthroline) two (trimethyl silicon based-1-propane sulfonic acid of 3-) changes ruthenium) embedding, adopt the fluorescence spectrum figure that the optical excitation of 470nm obtains;
Fig. 4 is under HPTS is dissolved in solid conditions, carries out exciting the spectrogram obtained with the light of 470nm;
Fig. 5, after HPTS and amino modified p-HEMA covalency are fixed, carries out with 470nm exciting the spectrogram obtained;
Fig. 6 is after HPTS and amino modified p-HEMA covalency are fixed, when 550nm absorbs, to the absorbing state spectrogram of exciting light.
In figure: 1-optical fiber probe, 2-polyurethane hydrogel layer, the responsive particulate of 3-pH, the responsive particulate of 4-oxygen.
Embodiment
Below in conjunction with the accompanying drawing in the present invention, the technical scheme in the present invention is clearly and completely described.
Figure 1 shows that the present invention monitors the structural representation of the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen, the two-parameter fluorescent optical fiber sensor probe of single-point of described monitoring pH value and partial pressure of oxygen comprises optical fiber probe 1, the responsive particulate 3 of pH being fixed on the polyurethane hydrogel layer 2 on optical fiber probe 1 and be embedded in polyurethane hydrogel layer 2 and the responsive particulate 4 of oxygen, wherein the responsive particulate 3 of pH passes through HPTS (8-hydroxyl pyrene-1, 3, 6-trisulfonic acid trisodium salt) covalency is fixed on amino modified p-HEMA (amino modified poly hydroxyethyl methylacrylate) and is prepared from, to avoid the spilling of indicator, the responsive particulate 4 of oxygen passes through solvent methenyl choloride by Ru (dpp)
3 2+be embedded in organic modified silicate to be prepared from, to obtain better selectivity and stability, the application of organic modified silicate preferably resolves crackle and hydrophilic problem, also remains the advantage of organic modified silicate masking simultaneously.
(1) synthesis of amino modified p-HEMA
Get a certain amount of toluene and ethanolamine hydrochloric salt, the mass ratio of toluene and ethanolamine hydrochloric salt is 4 ~ 6:1, joins in three-neck flask, stirs and after being heated to 100 DEG C ~ 150 DEG C, slowly dropwise drips appropriate methacrylic chloride.After dropwising, continue stirring 2 ~ 5 hours, be cooled to 10 DEG C to-20 DEG C.After solid is separated out, filter, the filter residue toluene of same dosage or diisopropyl ether.Decompression drying, obtains amino modified p-HEMA.
(2) synthesis of the responsive particulate 3 of pH
Get amino modified p-HEMA (amino modified poly hydroxyethyl methylacrylate) and HPTS (the 8-hydroxyl pyrene-1 of preparation in 200mg ~ 500mg (1), 3,6-trisulfonic acid trisodium salt) be dissolved in the distilled water of 100mL ~ 500mL, wherein amino modified poly hydroxyethyl methylacrylate and 8-hydroxyl pyrene-1,3, the mass ratio of 6-trisulfonic acid trisodium salt is between 50:1 to 70:1, stir about is after ten minutes, add the EDC (1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride) of 5mg-100mg, then stir about 2 ~ 5 hours.Then use distilled water, pH is 4 damping fluids, and pH is that 9 damping fluids and alcohol wash successively until colourless.Sediment is placed on ready glass sheet, dries.With sand paper by the polymkeric substance polishing on glass sheet, pulverize, the responsive particulate of pH can be obtained.
Amino modified p-HEMA synthesis based on this method is relatively easy to be realized and relatively cheap, then by the fixing mode of covalency, pH indicator HPTS covalency is fixed in p-HEMA the synthesis realizing the responsive particulate of pH.Fig. 4 and Fig. 5 is that the emission wavelength of the fluorescence spectrum figure that the light fixing front and back 470nm to pH indicator covalency excites is all at 542nm place.Fig. 6 be then confirm covalency fix after the maximum excitation of pH indicator still at 470nm.Draw by detecting, after covalency is fixing, excitation peak and the absorption peak of pH indicator are not moved.
(3) synthesis of organic modified silicate
Organic modified silicate is prepared according to trimethoxy-benzene base silane and trimethyl methoxy silane molar ratio 10 ~ 20:1.Shown by table 1 and compared by test, the present inventor found when trimethoxy-benzene base silane and trimethyl methoxy silane molar ratio are 18:1 time, the organic modified silicate performance obtained by the method is best, have good optical stability, and the large I of particulate actual effect according to the present invention controls.
The different trimethoxy-benzene base silane of table 1 and trimethyl methoxy silane molar ratio obtain the performance of the responsive particulate of oxygen
The hydrochloric acid of configuration 0.1mol/L, the ethanol getting 25mL ~ 100mL is put in round-bottomed flask, the trimethoxy-benzene base silane getting same dosage is again dissolved in ethanol, mixes, then is dripped to by the hydrochloric acid of the 0.1mol/L configured in round-bottomed flask and (provide the environment that acid).Round-bottomed flask is put into the water-bath of 65 DEG C ~ 100 DEG C.Continue 2.5 ~ 5 hours, add trimethyl methoxy silane according to trimethoxy-benzene base silane and trimethyl methoxy silane molar ratio 18:1, reaction continues after 1 ~ 3 hour again, cooling.After round-bottomed flask thoroughly cools, the distilled water adding 2/3 round-bottomed flask capacity stops carrying out further of reaction.Round-bottomed flask is left standstill 8 ~ 12 hours, grease is fully precipitated formed after latex to remove aqueous phase, latex to be placed in the drying box of 150 DEG C ~ 200 DEG C dry 5 ~ 8 hours.In order to obtain the better organic modified silicate of performance, solid above-mentioned steps obtained is placed in the drying box of 200 DEG C ~ 280 DEG C, and with the air in vacuum pump drying box, dry 12 ~ 15 hours, then crushed into powder shape can obtain organic modified silicate.
(4) synthesis of the responsive particulate 4 of oxygen
Get the Ru (dpp) of 5mg-100mg
3cl
2(three (4,7-biphenyl-1,10-phenanthroline) ruthenous chloride) with Na-TMS (3-trimethyl silicon based-1-propane sulfonic acid sodium salt) in separating funnel, wherein three (4,7-biphenyl-1,10-phenanthroline) mol ratio of ruthenous chloride and 3-trimethyl silicon based-1-propane sulfonic acid sodium salt is less than 1:2, and the distilled water adding 50mL ~ 200mL mixes.Then add appropriate chloroform (5/4 of distilled water), extraction, obtains Ru (dpp)
3(TMS)
2chloroformic solution.The organic modified silicate of appropriate (4-10 of distilled water volume doubly) is put into the Ru (dpp) that 20mL ~ 100mL is housed
3(TMS)
2chloroformic solution, make it disperse fully, stir, then use ethanol wash, centrifugal mixer.Sediment is placed on ready glass sheet, dries.With sand paper by the polymkeric substance polishing on glass sheet, pulverize, obtain the responsive particulate of oxygen.
The response speed of the responsive particulate of oxygen to oxygen of synthesizing based on this method is also obviously accelerated, and can not affect Ru (dpp)
3(TMS)
2fluorescent quenching.As shown in Figures 2 and 3, be for Ru (dpp)
3(Cl)
2particulate responsive to the oxygen used after organic modified silicate embedding, fluorescence spectrophotometer carries out exciting the fluorescence spectrum figure made with the blue light of 470nm.
(5) the responsive particulate 3 of pH and the responsive particulate 4 of oxygen disperse to embed polyurethane hydrogel layer 2
Detailed process is get the polyurethane hydrogel of 5mg ~ 100mg and appropriate alcoholic solution (alcohol and water volume ratio are 9:1) mixes, and alcoholic solution and polyurethane hydrogel are configured to polyurethane hydrogel solution according to mass ratio 19:1.Get the Ru (dpp) of 10mg ~ 100mg
3 2+the HPTS/p-HEMA particulate (i.e. the responsive particulate 3 of pH) of/ormosil particulate (i.e. the responsive particulate 4 of oxygen) and 14mg ~ 150mg is uniformly distributed in 300mg ~ 500mg polyurethane hydrogel solution, and stirring is spent the night.By the fibre-optical probe top-submerged of 1000nm in above-mentioned mixed solution, be at room temperature placed on dry 24h in atmospheric environment subsequently, namely complete the making of the two-parameter fluorescent optical fiber sensor probe of single-point of the present invention.
Principle of the present invention utilizes two kinds of different indicator (HPTS, Ru (dpp)
3 2+) there is identical absorption peak, different fluorescence lifetime, the fluorescence lifetime of pH indicator HPTS is ns level, oxygen indicator Ru (dpp)
3 2+fluorescence lifetime be us level, utilize LED light source under double frequency timesharing excites, adopt low frequency phase modulation method to realize pH value determination and partial pressure of oxygen simultaneously.Concrete, the present invention adopts two indicator of fluorescence lifetime significant difference: pH indicator HPT (peak value excitation/emission ripple 468/542nm) is ns level short life indicator, oxygen indicator Ru (dpp)
3 2+(peak value excitation/emission wavelength 468/608nm) is us level long-life indicator, and under exciting light Sine Modulated, the utilizing emitted light with two indicator of different fluorescence lifetime is also same frequency sine-wave.Under the low modulation frequencies of kHz scope, the radiative amplitude of short-life indicator changes with tested pH value, and phase place remains unchanged, and the radiative amplitude of long-life indicator and phase place are all with tested pO
2change, if measure the total phase shift under two different modulating frequencies simultaneously, just can parse this two tested parameters.Application of the present invention can be generalized to the fields such as cell chulture, biofermentation, marine ecology, monitoring water quality, food hygiene from biomedical clinical.
As shown in table 2 is actual effect of the present invention checking, and actual verification method of the present invention tests the result that pH is the gas and vapor permeation gas test passing into different partial in the solution of 7.53,6.86,4 respectively.The composition of mixed gas is the mixed gas of oxygen and nitrogen, and actual test passes into the mixed gas that partial pressure of oxygen is 5kPa and 15kPa respectively.Under the driving frequency of LED is respectively 30KHz and 60KHz situation, obtain the actual phase shift of drive singal and the change of amplitude by digital lock-in amplifier, obtain the pH of solution and the actual measured value of partial pressure of oxygen through corresponding data processing subsequently.
The actual verification result of the mixed gas of different partial (kPa) is passed in the different pH solution of table 2
Can from table 2, use sensor probe of the present invention can record pH and partial pressure of oxygen simultaneously, and error is less, and the partial pressure of oxygen recorded in the solution of different pH is relatively stable, and the pH recorded in the pH solution passing into different partial does not have greatly changed along with the change of partial pressure of oxygen yet.So can draw from measurement data, while monitoring two parameter at the same time, between two parameter, do not have obvious measurements interference.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, anyly belongs to those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (6)
1. monitor the two-parameter fluorescent optical fiber sensor probe of single-point of pH value and partial pressure of oxygen for one kind, comprise optical fiber probe, be fixed on polyurethane hydrogel layer on optical fiber probe and dispersion and be embedded in the responsive particulate of pH in polyurethane hydrogel layer and the responsive particulate of oxygen, it is characterized in that: the responsive particulate of described pH is prepared from by HPTS covalency is fixed on amino modified p-HEMA, the responsive particulate of described oxygen passes through solvent methenyl choloride by Ru (dpp)
3 2+be embedded in organic modified silicate to be prepared from.
2. the two-parameter fluorescent optical fiber sensor probe of the single-point of monitoring pH value as claimed in claim 1 and partial pressure of oxygen, it is characterized in that: amino modified p-HEMA is prepared from by following steps: get a certain amount of toluene and ethanolamine hydrochloric salt, according to toluene: the mass ratio 4 ~ 6:1 of ethanolamine hydrochloric salt joins in three-neck flask, to stir and after being heated to 100 DEG C ~ 150 DEG C, slowly dropwise drip appropriate methacrylic chloride, after dropwising, continue stirring 2 ~ 5 hours, be cooled to 10 DEG C to-20 DEG C, after solid is separated out, filter, the filter residue toluene of same dosage or diisopropyl ether, decompression drying, amino modified p-HEMA can be obtained.
3. the two-parameter fluorescent optical fiber sensor probe of the single-point of monitoring pH value as claimed in claim 1 or 2 and partial pressure of oxygen, it is characterized in that: the responsive particulate of pH is prepared from by following steps: get the amino modified p-HEMA of 200mg ~ 500mg and be dissolved in the distilled water of 100mL ~ 500mL, then the HPTS getting 4mg ~ 10mg adds during mixing is dissolved in, stir after ten minutes, the EDC adding 5mg ~ 100mg stirs 2 ~ 5 hours again, then distilled water is used, pH is the damping fluid of 4, pH is the damping fluid of 9, alcohol washs until colourless successively, sediment is placed on ready glass sheet, dry, with sand paper by the polymkeric substance polishing on glass sheet, pulverize, the responsive particulate of pH can be obtained.
4. the two-parameter fluorescent optical fiber sensor probe of the single-point of monitoring pH value as claimed in claim 1 and partial pressure of oxygen, it is characterized in that: organic modified silicate is prepared from by following steps: the hydrochloric acid of configuration 0.1mol/L, the ethanol getting 25mL ~ 100mL is put in round-bottomed flask, the trimethoxy-benzene base silane getting same dosage is again dissolved in ethanol, mix, again the hydrochloric acid of the 0.1mol/L configured is dripped in round-bottomed flask, round-bottomed flask is put into the water-bath of 65 DEG C ~ 100 DEG C, continue 2.5 ~ 5 hours, trimethyl methoxy silane is added according to trimethoxy-benzene base silane and trimethyl methoxy silane molar ratio 10 ~ 20:1, reaction continues after 1 ~ 3 hour again, cooling, after round-bottomed flask thoroughly cools, the distilled water adding 2/3 round-bottomed flask capacity stops carrying out further of reaction, round-bottomed flask is left standstill 8 ~ 12 hours, aqueous phase is removed after making grease fully precipitate formation latex, latex to be placed in the drying box of 150 DEG C ~ 200 DEG C dry 5 ~ 8 hours, crushed into powder shape can obtain organic modified silicate.
5. the monitoring pH value as described in claim 1 or 4 and the two-parameter fluorescent optical fiber sensor probe of the single-point of partial pressure of oxygen, is characterized in that: the responsive particulate of oxygen is prepared from by following steps: the Ru (dpp) getting 5mg ~ 100mg
3cl
2with Na-TMS in separating funnel, wherein Ru (dpp)
3cl
2be less than 1:2 with the mol ratio of Na-TMS, the distilled water adding 50mL ~ 200mL mixes, and then adds the chloroform extraction of distilled water volume 5/4 times, obtains Ru (dpp)
3(TMS)
2chloroformic solution, the organic modified silicate of distilled water volume 4 ~ 10 times is put into the Ru (dpp) that 20mL ~ 100mL is housed
3(TMS)
2chloroformic solution, make it disperse fully, stir, then use ethanol wash, centrifugal mixer, sediment is placed on ready glass sheet, dries, with sand paper by the polymkeric substance polishing on glass sheet, pulverize, obtain the responsive particulate of oxygen.
6. the two-parameter fluorescent optical fiber sensor probe of the single-point of monitoring pH value as claimed in claim 1 and partial pressure of oxygen, it is characterized in that: the responsive particulate of pH and the responsive microparticulate of oxygen embed polyurethane hydrogel layer concrete steps and be: polyurethane hydrogel and the appropriate alcoholic solution of getting 5mg-100mg mix, in alcoholic solution, alcohol and water volume ratio are 9:1, alcoholic solution and polyurethane hydrogel are configured to polyurethane hydrogel solution according to mass ratio 19:1, the responsive particulate homogenous of pH of the responsive particulate of oxygen and 14mg ~ 150mg of getting 10mg ~ 100mg is distributed in 300mg ~ 500mg polyurethane hydrogel solution, stirring is spent the night.
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| CN108351303B (en) * | 2015-11-23 | 2022-05-17 | 珀金埃尔默健康科学公司 | 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 fluorescence sensor as well as preparation method and application thereof |
| CN108572165A (en) * | 2018-06-19 | 2018-09-25 | 南京大学 | A kind of pH tablets 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 |
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| CN104764725B (en) | 2017-11-24 |
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