CN106085410A - PEI modified carbon point FITC complex is as ratio fluorescent pH probe and Cu2+the application of fluorescent probe - Google Patents

PEI modified carbon point FITC complex is as ratio fluorescent pH probe and Cu2+the application of fluorescent probe Download PDF

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CN106085410A
CN106085410A CN201610429533.0A CN201610429533A CN106085410A CN 106085410 A CN106085410 A CN 106085410A CN 201610429533 A CN201610429533 A CN 201610429533A CN 106085410 A CN106085410 A CN 106085410A
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fitc
carbon point
pei
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cds
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桂日军
金辉
朱欣欣
徐显朕
王宗花
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Qingdao University
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Abstract

The invention discloses PEI modified carbon point FITC complex as ratio fluorescent pH probe and Cu2+The application of fluorescent probe.The present invention uses cherry tomato to be raw material, prepares fluorescence by Hydrothermal Synthesis and pH is changed insensitive carbon point, and PEI modifies CDs then, and the amino on PEI reacts with isosulfocyanate radical on FITC molecule, forms complex.The response that in complex, pH is changed by the fluorescence of FITC is high, and ratio probes based on CDs and FITC fluorescence detects for pH;Amino on PEI and Cu2+Coordination is occurred to make the fluorescence intensity of CDs Yu FITC with Cu in solution2+Concentration raises and declines, it is achieved detection Cu2+.The plurality of advantages such as the fluorescent probe selection that the present invention builds is novel, it is highly sensitive to have, selectivity good, simple to operate, range of linearity width, detection limit are low, can be used for pH and Cu in aqueous solution and biological sample2+Efficient detection.

Description

PEI modified carbon point-FITC complex is as ratio fluorescent pH probe and Cu2+Fluorescence is visited The application of pin
Technical field
The invention belongs to the crossing domain of chemistry, biology and materialogy, relate to material prepare, biological and environment ion inspection Survey and pH detection, be specifically related to the preparation of PEI modified carbon point-FITC complex and its as ratio fluorescent pH probe and Cu2+The application of fluorescent probe.
Background technology
Quantum dot typically refers to be smaller in size than or close to the semiconductor nano of its Exciton Bohr Radius, is that a class has solely The nanoparticle of special optical, electrical characteristic.Compared with one-dimensional or Two-dimensional Carbon nano material, use carbon point prepared by nontoxic biological raw material (CDs) having higher specific surface area and more edge active site, this makes CDs compare large-size carbon material at bio-sensing More extensive and efficient application prospect has been possessed with catalytic field.Additionally, the photoluminescent property of CDs is better than repairing without group after amination The CDs of decorations, and polymine (PEI) can regulate and control its optical property as the nitrogen source of CDs.In addition, PEI is as one Polyamine family macromolecule has good coordination to metal ion so that it is have in ion detection, biomedicine and imaging field Having important application, correlational study has become one of current study hotspot.
H in solution+Concentration or pH value are the important parameters characterizing SOLUTION PROPERTIES, and it not only affects other materialization of solution Matter, also affects response speed and direction simultaneously, therefore, the measurement of pH value industrial and agricultural production, medicine, biological engineering, environment and The fields such as scientific research are significant.Comparing traditional pH reagent paper and the detection of pH glass electrode, photochemistry pH sensor is then There is advantages such as can reusing, the time is fast, volume is little, electromagnetism interference performance is strong, pollution-free, all kinds of chemical reactions, The aspects such as the telemetry and telecommand of environmental monitoring, biomedical sector and the dangerous situation such as underground mine, weapon test have wide Application prospect.Fluorescein isothiocyanate (FITC) is widely used in biomedical sector as fluorescent probe, and FITC is as glimmering Light pH indicator its fluorescence intensity in the solution that pH is relatively low is little, and in the solution that pH is higher, its fluorescence intensity increases, detection spirit Sensitivity is high.
Cu2+In environmental area and biology or chemical system, play vital effect, effectively detect Cu2+ It is necessary.Literature research shows, the CDs that PEI modifies can specifically detect Cu2+, Yongqiang Dong etc. devises one Plant the fluorescent probe modifying CDs based on PEI, along with Cu2+Concentration increases, and CDs fluorescence intensity increases, and then can be to Cu2+It is fixed to carry out Measure fixed (Yongqiang Dong, Ruixue Wang, Geli Li, Congqiang Chen, Yuwu Chi, * and Guonan Chen., Anal.Chem., 2012,84,6220-6224).Goon, I.Y. etc. utilize the Fe that PEI modifies3O4NPs carrys out detection by quantitative Hg2+(Goon, I.Y., Zhang, C.C., Lim, M.;, Gooding, J.J., Amal, R.Langmuir 2010,26,12247- 12252).Fangkai Du etc. constructs FRET (fluorescence resonance energy transfer) pH sensor, and CDs supplies as Fluorescence Resonance Energy transfer Body, FITC is energy acceptor, it is achieved that to the Sensitive Detection of pH (Fangkai Du., Yunhao Ming., Fang Zeng., Changmin Yu and Shuizhu Wu.,Nanotechnology.,2013,24,365101)。
But above-mentioned detection major part pertains only to the detection of one pack system, and it is many to often relate to detect object in actual application Component detects, the heavy metal of such as sewage and pH value, generally requires multiple detection probe or detection equipment, so makes detection Loaded down with trivial details, so, explore a kind of multi-functional detection means and have a good application prospect.
Summary of the invention
For problem of the prior art, it is an object of the invention to provide a kind of multi-functional detection means to detect pH and Cu2+
For achieving the above object, the present invention relates to techniques below scheme:
First, the present invention provides a kind of PEI modified carbon point-FITC complex as ratio fluorescent pH probe and Cu2+Fluorescence The application of probe.
Described PEI modified carbon point-FITC complex: on the basis of PEI modified carbon point, further coupling FITC is prepared into Arrive;The preparation of PEI modified carbon point belongs to the state of the art, as Yongqiang Dong etc. (Yongqiang Dong, Ruixue Wang,Geli Li,Congqiang Chen,Yuwu Chi,and Guonan Chen.,Anal.Chem.2012, 84,6220-6224) disclosure, introduces the application in this together.
Preferably in technical scheme, PEI modified carbon point-FITC complex is prepared via a method which: molten to carbon point (CDs) Adding polymine (PEI) in liquid, mix homogeneously carries out the PEI of carbon point and modifies, and is subsequently adding Fluorescein isothiocyanate (FITC) carry out coupling, prepare PEI modified carbon point-FITC complex.
In preferred technical scheme, described carbon point (CDs) is prepared via a method which: squeezed the juice by cherry tomato, weigh β- Cyclodextrin powder adds in holy girl's fruit juice, stirs, autoclave hydro-thermal reaction, reactant centrifugation, collects upper strata dispersion Liquid, with membrane filtration, removes bulky grain;The filtrate of upper strata dispersion liquid is poured into rotary evaporation in Rotary Evaporators, adds third Ketone and ethanol extraction, separatory, centrifugation, lower sediment thing is carbon point (CDs).
Although about pH and Cu2+The preparation method of fluorescent probe existing document report, but so far, not yet have based on PEI modified carbon point-FITC composite is simultaneously used for detecting pH and Cu2+Domestic and foreign literature and patent report.The present invention On the basis of early-stage Study, find that PEI modified carbon point-FITC complex serves not only as ratio fluorescent pH probe and carries out pH Detection, and double fluorescent quenching based on CDs Yu FITC, can effectively detect Cu2+Concentration.Concrete, the present invention utilizes Amino on PEI, can not only be used for amination and modifies CDs, can react with isosulfocyanate radical on FITC by specificity again.Work as pH of buffer Time different, CDs fluorescence intensity is almost unchanged, therefore can be as reference, and FITC fluorescence intensity gradually rises with pH and increases, so CDs Yu FITC ratio fluorescent can be used for qualitative detection pH value of solution;The coupling of FITC Yu PEI modified carbon point, does not only interfere with PEI With Cu2+Coordination combine, and based on PEI and Cu2+Combination can cause the double fluorescence of CDs Yu FITC combined respectively at PEI Quenching effect, promotes detection signal, works as Cu2+In the presence of, Cu2+Can be specific binding with PEI, with Cu2+Concentration raises so that CDs with FITC fluorescence intensity decreases simultaneously, causes fluorescent quenching, matching system CDs and FITC fluorescence intensity and Cu2+Concentration Between relation, can build and detect pH and Cu based on CDs-FITC complex simultaneously2+Fluoroscopic examination means.
Secondly, the present invention provides a kind of detection pH and Cu2+Detection method, the method includes:
PEI modified carbon point-FITC complex is used for pH detection: PEI modified carbon point-FITC complex is slow from different pH's Rush liquid mixing, measure the ratio fluorescent intensity I of systemFITC/ICDs(IFITCFor FITC fluorescence intensity in the buffer of different pH Value, ICDsFor CDs fluorescence intensity level in the buffer of different pH), matching system ratio fluorescent intensity and the relation of pH, enter The detection of row pH value of solution to be measured;
PEI modified carbon point-FITC complex is used for Cu2+Detection: by the PEI modified carbon point identical pH of-FITC complex Buffer dilution, measure system fluorescence intensity, be subsequently adding Cu2+Hatching, then measure the fluorescence intensity of system, matching system CDs Yu FITC fluorescence intensity and Cu2+Relation between concentration, carries out solution C u to be measured2+The detection of concentration.
Described PEI modified carbon point-FITC complex: on the basis of PEI modified carbon point, further coupling FITC is prepared into Arrive, it is preferred that PEI modified carbon point-FITC complex is prepared via a method which: in carbon point (CDs) solution, add polyethylene Imines (PEI), mix homogeneously carries out the PEI of carbon point and modifies, is subsequently adding Fluorescein isothiocyanate (FITC) and carries out coupling, prepare PEI modified carbon point-FITC complex.
Preferably in technical scheme, described carbon point (CDs) is prepared via a method which: is squeezed the juice by cherry tomato, weighs β-ring Dextrin powder adds in holy girl's fruit juice, stirs, autoclave hydro-thermal reaction, reactant centrifugation, collects upper strata dispersion liquid, With membrane filtration, remove bulky grain;The filtrate of upper strata dispersion liquid is poured into rotary evaporation in Rotary Evaporators, add acetone and Ethanol extracts, and separatory, centrifugation, lower sediment thing is carbon point (CDs).
Concrete, cherry tomato is squeezed the juice and is placed in clean beaker, weigh a certain amount of beta-schardinger dextrin-powder and add holy girl In fruit juice, by magnetic agitation, autoclave hydro-thermal reaction, centrifugation, collect upper strata dispersion liquid, with membrane filtration, remove big Granule, pours in Rotary Evaporators by the filtrate of upper strata dispersion liquid, at a certain temperature rotary evaporation in flask without bright Aobvious liquid, adds acetone and ethanol extraction, separatory, centrifugation, repeat this step 3 time and more than, lower sediment thing is carbon Point (CDs).
The present invention uses cherry tomato and beta-schardinger dextrin-hydro-thermal method to prepare carbon point, explores new carbon point and prepares material, made Standby carbon point has excellent optical property, and quantum yield is high, and its fluorescence intensity is suitable to the need of relative broad range pH detection stability Want, and this preparation method technique is simple, efficiently, raw material is nontoxic, be easy to get.
The present invention provides a kind of detection pH and Cu2+The construction method of the detection system of concentration, comprises the steps:
1) cherry tomato is squeezed the juice it is placed in beaker, weigh beta-schardinger dextrin-powder and add in holy girl's fruit juice, stirred by magnetic force Mix, autoclave hydro-thermal reaction, centrifugation, collect upper strata dispersion liquid, with membrane filtration, remove bulky grain, by upper strata dispersion liquid Filtrate pour in Rotary Evaporators, without obvious liquid in rotary evaporation to flask, add acetone and ethanol extraction, separatory, Centrifugation, repeat this step 3 time and more than, lower sediment thing is carbon point (CDs);
2) in the CDs solution of preparation, add polymine (PEI), magnetic agitation under room temperature, add isothiocyanic acid glimmering Light element (FITC), continues magnetic agitation, prepares PEI modified carbon point-FITC complex;
3) the PEI modified carbon point-FITC complex of preparation is divided into two parts standby,
Part I PEI modified carbon point-FITC complex for pH detection system build: by CDs-FITC complex with not Mix with the phosphate buffer of pH, measure the ratio fluorescent intensity (I of systemFITC/ICDs), matching system ratio fluorescent intensity With the relation of pH, build pH ratio fluorescent probe in detecting system based on PEI modified carbon point-FITC complex;
Part II PEI modified carbon point-FITC complex is used for Cu2+Detection system builds: used by CDs-FITC complex The phosphate buffer dilution of identical pH, measures system fluorescence intensity, is subsequently adding variable concentrations Cu2+Hatching, then measure system Fluorescence intensity, matching system fluorescence intensity and Cu2+Relation between concentration, builds based on PEI modified carbon point-FITC complex Cu2+Fluorescent probe detection system.
Preferably in technical scheme, the concrete technology condition of step (1) is: the volume of holy girl's fruit juice is 10~100mL, β- The quality of cyclodextrin powder is 0.1~1.0g, and the time of magnetic agitation is 1~10min, and hydrothermal temperature is 100~200 DEG C, the hydro-thermal reaction time is 2~12h, the rotating speed of the centrifugation after hydro-thermal reaction and time is respectively 5000~16000rpm, 3~15min, the temperature set in Rotary Evaporators is as 25~80 DEG C, and the volume adding acetone is 5~50mL, adds ethanol Volume is 5~50mL, and the rotating speed of the centrifugation after separatory and time are respectively 5000~16000rpm, 3~15min.
Preferably in technical scheme, the concrete technology condition of step (2) is: CDs concentration and volume be respectively 0.1~ 1.0mgmL-1, 1~10mL, PEI mass fraction and volume be respectively 0.01~0.1%, 0.1~1.0mL, the magnetic agitation time is 30min~6h, FITC concentration and volume are respectively 0.01~0.1mM, 5~50mL, and the magnetic agitation time is 30min~3h.
Preferably in technical scheme, the concrete technology condition of step (3) is: Part I PEI modified carbon point-FITC is combined The volume of thing is 20~200 μ L, and the volume of 10mM phosphate buffered solution is 1~10mL, the pH of phosphate buffer be 3.2~ 9.0;The volume of Part II PEI modified carbon point-FITC composite is 20~200 μ L, phosphate buffered solution volume Being 1~10mL, the pH of phosphate buffer is 7.4, Cu2+Concentration be 0.01~10.0 μM, brooding time 1~10min.
The present invention achieves following beneficial effect:
(1) present invention discover that PEI modified carbon point-FITC complex serves not only as ratio fluorescent pH probe and carries out pH's Detection, and double fluorescent quenching based on CDs Yu FITC, can effectively detect Cu2+Concentration, provides a kind of multi-functional for this Detection means, and in order to expand the H of FITC+Sensor range of application, increase sensor service life and improve sensitive Degree, the present invention devises ratio fluorescent sensor based on CDs-FITC and detects pH and Cu for simultaneously2+
(2) present invention uses new carbon point to prepare material, and prepared carbon point has excellent optical property, and it is wider Scope pH is stable, passes through IFITC/ICDsThe detection of ratio fluorescent intensity, can improve Detection accuracy and detection efficiency.
(3) the inventive method mild condition, equipment is simple, easily operated, CDs-FITC complex can pass through Hydrothermal Synthesis Method, rotary evaporation purifies and directly prepares, and raw material availability is high, low cost.
(4) the invention provides that a kind of technique is simple, productivity is high, production cost is low, environmental protection, be easy to operate and control A kind of based on carbon point/Fluorescein isothiocyanate complex ratio fluorescent pH probe and Cu2+The system of fluorescent probe detection system Preparation Method, compared with prior art, probe in detecting system of the present invention has highly sensitive, detection range width, and detection limit is low etc. excellent Point, having a extensive future of the fields such as biochemical analysis, medical diagnosis, environmental monitoring.
Accompanying drawing explanation
Fig. 1 ratio fluorescent based on carbon point/Fluorescein isothiocyanate complex pH probe and Cu2+The preparation side of fluorescent probe Method and principle schematic thereof;
Fig. 2: PEI modified carbon point-FITC complex fluorescence emission spectrum under condition of different pH;
The ratio fluorescent intensity of Fig. 3: PEI modified carbon point-FITC complex and the Linear Fit Chart of corresponding pH;
Fig. 4: PEI modified carbon point-FITC complex is at variable concentrations Cu2+In the presence of fluorescence emission spectrogram;
FITC and CDs relative intensity of fluorescence and corresponding Cu in Fig. 5: PEI modified carbon point-FITC complex2+Line under concentration Property fitted figure.
Detailed description of the invention
Mode by the following examples further illustrates the present invention, but the most therefore limits the present invention to described reality Execute among example scope.The experimental technique of unreceipted actual conditions in the following example, conventionally selects with condition Select.
Embodiment 1
Use juice extractor to squeeze fresh holy girl fruit juice 30mL, be placed in clean beaker;Weigh 0.5g beta-schardinger dextrin-powder Add in holy girl's fruit juice, magnetic agitation 5min, transposition autoclave hydro-thermal reaction 5h, reaction temperature 120 DEG C;Reaction is centrifugal after terminating Separating (10000rpm, 15min), collect upper strata dispersion liquid, filter membrane filters, and removes bulky grain;Upper strata dispersion liquid is poured into In Rotary Evaporators, at a temperature of 40 DEG C rotary evaporation in flask without obvious liquid, be separately added into acetone and the second of 20mL Alcohol, centrifugation (12000rpm, 5min);Repeating this centrifugation step three times, lower sediment thing is CDs;Preparation 1.0mg mL- 1CDs aqueous solution 10mL, adds the PEI 0.2mL of 0.1%, magnetic agitation 0.5h under room temperature;Add the FITC 10mL of 0.05mM Continue magnetic agitation 1h and prepare PEI modified carbon point-FITC complex.
The complex of above-mentioned preparation is divided into two parts: a part detects for pH, the PEI modified carbon point-FITC of 200 μ L The 10mM phosphate buffer mixing of complex pH different from 3mL (3.2~9.0);The fluorescence intensity of measurement system, matching system Ratio fluorescent intensity and the relation of pH, build pH ratio fluorescent probe in detecting body based on PEI modified carbon point-FITC complex System.It is additionally useful for Cu2+Detection, by 200 μ L PEI modified carbon point-FITC complex with 3mL phosphate buffer (10mM, PH7.4) dilution, measures the fluorescence intensity of system, is subsequently adding 0.01~10.0 μM of Cu2+Hatching 10min, then measure system Fluorescence intensity, matching system fluorescence intensity and Cu2+Relation between concentration, builds based on PEI modified carbon point-FITC complex Cu2+Fluorescent probe detection system.
Embodiment 2
Use juice extractor to squeeze fresh holy girl fruit juice 50mL, be placed in clean beaker;Weigh 0.7g beta-schardinger dextrin-powder Add in holy girl's fruit juice, magnetic agitation 7min, transposition autoclave hydro-thermal reaction 3h, reaction temperature 140 DEG C;Reaction is centrifugal after terminating Separating (12000rpm, 10min), collect upper strata dispersion liquid, filter membrane filters, and removes bulky grain;Upper strata dispersion liquid is poured into In Rotary Evaporators, at a temperature of 60 DEG C rotary evaporation in flask without obvious liquid, be separately added into acetone and the second of 30mL Alcohol, centrifugation (12000rpm, 10min);Repeating this centrifugation step three times, lower sediment thing is CDs;Preparation 0.5mg mL-1CDs aqueous solution 10mL, adds the PEI 0.1mL of 0.1%, magnetic agitation 1h under room temperature;The FITC 5mL adding 0.05mM continues Continuous magnetic agitation 2h prepares PEI modified carbon point-FITC complex.
The complex of above-mentioned preparation is divided into two parts: a part detects for pH, the PEI modified carbon point-FITC of 100 μ L The 10mM phosphate buffer mixing of complex pH different from 2mL (3.2~9.0);The fluorescence intensity of measurement system, matching system Ratio fluorescent intensity and the relation of pH, build pH ratio fluorescent probe in detecting body based on PEI modified carbon point-FITC complex System.It is additionally useful for Cu2+Detection, dilutes 100 μ L CDs-FITC complex 5mL phosphate buffer (10mM, pH7.4), surveys The fluorescence intensity of amount system, is subsequently adding 0.01~10.0 μM of Cu2+Hatching 10min, then measure the fluorescence intensity of system, matching System fluorescence intensity and Cu2+Relation between concentration, builds Cu based on PEI modified carbon point-FITC complex2+Fluorescent probe is examined Survey system.
Embodiment 3
Use juice extractor to squeeze fresh holy girl fruit juice 80mL, be placed in clean beaker;Weigh 0.8g beta-schardinger dextrin-powder Add in holy girl's fruit juice, magnetic agitation 10min, transposition autoclave hydro-thermal reaction 6h, reaction temperature 140 DEG C;Reaction terminate after from The heart separates (12000rpm, 10min), collects upper strata dispersion liquid, and filter membrane filters, and removes bulky grain;Upper strata dispersion liquid is fallen Enter in Rotary Evaporators, at a temperature of 60 DEG C rotary evaporation in flask without obvious liquid, be separately added into 20mL acetone and Ethanol, centrifugation (12000rpm, 10min);Repeating this centrifugation step three times, lower sediment thing is CDs;Preparation 0.5mg mL-1CDs aqueous solution 10mL, adds the PEI 0.2mL of 0.1%, magnetic agitation 1h under room temperature;The FITC 5mL adding 0.05mM continues Continuous magnetic agitation 2h prepares PEI modified carbon point-FITC complex.
The complex of above-mentioned preparation is divided into two parts: a part detects for pH, the PEI modified carbon point-FITC of 150 μ L The 10mM phosphate buffer mixing of complex pH different from 5mL (3.2~9.0);The fluorescence intensity of measurement system, matching system Ratio fluorescent intensity and the relation of pH, build pH ratio fluorescent probe in detecting body based on PEI modified carbon point-FITC complex System.It is additionally useful for Cu2+Detection, by 150 μ L PEI modified carbon point-FITC complex with 5mL phosphate buffer (10mM, PH7.4) dilution, measures the fluorescence intensity of system, is subsequently adding 0.01~10.0 μM of Cu2+Hatching 10min, then measure system Fluorescence intensity, matching system fluorescence intensity and Cu2+Relation between concentration, builds based on PEI modified carbon point-FITC complex Cu2+Fluorescent probe detection system.
Above-mentioned detection probe is 4.6~7.7 for the pH detection range of linearity;Cu2+Detection is in the range of 0.01~12.45 μM It is 7nM with Monitoring lower-cut.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art Member, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should be regarded as Protection scope of the present invention.

Claims (10)

1.PEI modified carbon point-FITC complex is as ratio fluorescent pH probe and Cu2+The application of fluorescent probe, described PEI modifies Carbon point-FITC complex is on the basis of PEI modified carbon point, the complex that further coupling FITC prepares.
Application the most according to claim 1, it is characterised in that PEI modified carbon point-FITC complex is made by the following method Standby: to add polymine (PEI) in carbon point (CDs) solution, mix homogeneously carries out the PEI of carbon point and modifies, and is subsequently adding different Hydrogen thiocyanate fluorescein (FITC) carries out coupling, prepares PEI modified carbon point-FITC complex.
Application the most according to claim 1 and 2, it is characterised in that carbon point (CDs) is prepared via a method which: by holy girl Fruit is squeezed the juice, and weighs beta-schardinger dextrin-powder and adds in holy girl's fruit juice, stirs, autoclave hydro-thermal reaction, reactant centrifugation, Collect upper strata dispersion liquid, with membrane filtration, remove bulky grain;The filtrate of upper strata dispersion liquid is poured in Rotary Evaporators and rotate Evaporation, adds acetone and ethanol extraction, and separatory, centrifugation, lower sediment thing is carbon point (CDs).
4. detection pH and Cu2+Detection method, the method includes:
Described PEI modified carbon point-FITC complex is on the basis of PEI modified carbon point, and further coupling FITC prepares Complex,
PEI modified carbon is selected-FITC complex and is used for pH detection: PEI modified carbon selects the buffer of-FITC complex and different pH Mixing, measures the ratio fluorescent intensity I of systemFITC/ICDs, matching system ratio fluorescent intensity and the relation of pH, carry out to be measured molten The detection of liquid pH;
PEI modified carbon point-FITC complex is used for Cu2+Detection: by PEI modified carbon point-FITC complex delaying with identical pH Rush liquid dilution, measure system fluorescence intensity, be subsequently adding Cu2+Hatching, then measure the fluorescence intensity of system, matching system fluorescence is strong Degree and Cu2+Relation between concentration, carries out solution C u to be measured2+The detection of concentration.
Method the most according to claim 4, it is characterised in that PEI modified carbon point-FITC complex is made by the following method Standby: to add polymine (PEI) in carbon point (CDs) solution, mix homogeneously carries out the PEI of carbon point and modifies, and is subsequently adding different Hydrogen thiocyanate fluorescein (FITC) carries out coupling, prepares PEI modified carbon point-FITC complex.
6. according to the method described in claim 4 or 5, it is characterised in that carbon point (CDs) is prepared via a method which: by holy girl Fruit is squeezed the juice, and weighs beta-schardinger dextrin-powder and adds in holy girl's fruit juice, stirs, autoclave hydro-thermal reaction, reactant centrifugation, Collect upper strata dispersion liquid, with membrane filtration, remove bulky grain;The filtrate of upper strata dispersion liquid is poured in Rotary Evaporators and rotate Evaporation, adds acetone and ethanol extraction, and separatory, centrifugation, lower sediment thing is carbon point (CDs).
7. detection pH and Cu2+The construction method of the detection system of concentration, comprises the steps:
1) cherry tomato is squeezed the juice it is placed in beaker, weigh beta-schardinger dextrin-powder and add in holy girl's fruit juice, by magnetic agitation, high Pressure still hydro-thermal reaction, centrifugation, collect upper strata dispersion liquid, with membrane filtration, remove bulky grain, by the filtration of upper strata dispersion liquid Liquid is poured in Rotary Evaporators, without obvious liquid in rotary evaporation to flask, adds acetone and ethanol extraction, separatory, is centrifuged and divides From, repeat this step 3 time and more than, lower sediment thing is carbon point (CDs);
2) in the CDs solution of preparation, add polymine (PEI), magnetic agitation under room temperature, add Fluorescein isothiocyanate (FITC), continue magnetic agitation, prepare PEI modified carbon point-FITC complex;
3) the PEI modified carbon point-FITC complex of preparation is divided into two parts standby,
Part I PEI modified carbon point-FITC complex builds for pH detection system: by CDs-FITC complex and different pH Phosphate buffer mixing, measure system ratio fluorescent intensity (IFITC/ICDs), matching system ratio fluorescent intensity and pH Relation, build pH ratio fluorescent probe in detecting system based on PEI modified carbon point-FITC complex;
Part II PEI modified carbon point-FITC complex is used for Cu2+Detection system builds: by CDs-FITC complex with identical The phosphate buffer dilution of pH, measures system fluorescence intensity, is subsequently adding variable concentrations Cu2+Hatching, then measure the glimmering of system Light intensity, matching system fluorescence intensity and Cu2+Relation between concentration, builds Cu based on PEI modified carbon point-FITC complex2+ Fluorescent probe detection system.
Method the most according to claim 7, it is characterised in that the concrete technology condition of step (1) is: the body of holy girl's fruit juice Long-pending is 10~100mL, and the quality of beta-schardinger dextrin-powder is 0.1~1.0g, and the time of magnetic agitation is 1~10min, hydro-thermal reaction Temperature is 100~200 DEG C, and the hydro-thermal reaction time is 2~12h, and after hydro-thermal reaction, rotating speed and the time of centrifugation are respectively 5000~16000rpm, 3~15min, the temperature set in Rotary Evaporators as 25~80 DEG C, add acetone volume be 5~ 50mL, the volume adding ethanol is 5~50mL, and after separatory, rotating speed and the time of centrifugation are respectively 5000~16000rpm, 3 ~15min.
Method the most according to claim 7, it is characterised in that the concrete technology condition of step (2) is: CDs concentration and body Long-pending respectively 0.1~1.0mg mL-1, 1~10mL, PEI mass fraction and volume be respectively 0.01~0.1%, 0.1~1.0mL, The magnetic agitation time is 30min~6h, and FITC concentration and volume are respectively 0.01~0.1mM, 5~50mL, magnetic agitation time For 30min~3h.
Method the most according to claim 7, it is characterised in that the concrete technology condition of step (3) is: Part I PEI The volume of modified carbon point-FITC complex is 20~200 μ L, and the volume of 10mM phosphate buffered solution is 1~10mL, phosphate The pH of buffer is 3.2~9.0;The volume of Part II PEI modified carbon point-FITC composite is 20~200 μ L, phosphorus Hydrochlorate volume of buffer solution is 1~10mL, and the pH of phosphate buffer is 7.4, Cu2+Concentration be 0.01~10.0 μM, hatching Time 1~10min.
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