CN105911039B - A method of trivalent chromic ion is detected using rhodamine fluorescence probe - Google Patents
A method of trivalent chromic ion is detected using rhodamine fluorescence probe Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
Abstract
The present invention provides a kind of methods using rhodamine fluorescence probe detection trivalent chromic ion, it is characterized in that, it include: the trivalent chromic ion solution for preparing various concentration, it stands, under conditions of excitation wavelength is 560nm, the fluorescence intensity that detection launch wavelength is 582nm, using the concentration of chromium ion as abscissa, fluorescence intensity is ordinate mapping, obtains linear relationship curve；Rhodamine fluorescence probe solution is added to NaOH/NaH2PO4The buffer system containing fluorescence probe is obtained in buffer solution, trivalent chromic ion solution to be measured is added, is stood, and under conditions of excitation wavelength is 560nm, the fluorescence intensity that detection launch wavelength is 582nm calculates the concentration of chromium ion according to linear relationship curve.Fluorescence probe energy Selective recognition trivalent chromic ion of the present invention, and it is not high by the interference of other common ions, fluorescence intensity height, fluorescence intensity.
Description
Technical field
The invention belongs to fluorescence probe material detection method fields, in particular to a kind of to be examined using rhodamine fluorescence probe
The method for surveying trivalent chromic ion.
Background technique
Chromium is element common in a kind of nature, widely distributed on earth.The chemical combination of common chromium compound
Valence is mainly+3 ,+6 valences, it has of crucial importance in terms of guaranteeing human health, coordinate plant growth, promoting
Effect.In terms of human health, trivalent chromium is the essential element of balanced human and animal diet followed, human body and animal body per extremely big
General demand 50-200 μ g.Also, trivalent chromium plays vital in the metabolism of carbohydrate, protein, fat and nucleic acid
Effect.Firstly, chromium can inhibit to be mutated, there is certain protective effect on cancer risk；Secondly, the adjustable glycometabolism of chromium, centainly
It can prevent diabetes in degree；Furthermore the adjustable fat metabolism of chromium, can reduce containing for cholesterol and triglyceride
Amount.In terms of coordinate plant growth, micro chromium can make the activity of enzyme in plant be improved, and the light of plant can be improved
Cooperation is used, and enhancing plant is to the resistivity of disease and then the yield of raising crops.In industrial aspect, chromium is industrial production mistake
Must be indispensable in journey, such as leather manufacture, coating, timber preservative, pigment etc., wherein metal is widely applied in trivalent chromium
The industries such as the heat treatment of material, metal working material, metal material, trivalent chromium content are most important to quality of coating.Currently, I
The content of trivalent chromium is 0.5mg/L in water in state's earth's surface, which can satisfy the demand of normal chromium in human body, excessive chromium
Ion pair human health will cause injury.As the improvement of people's living standards, making to get in a large amount of uses of architectural constructional materials
Carry out more chromium exposures in the environment, this is a kind of burden to environment, while being also that there are a kind of potential prestige to human health
The side of body.Therefore, it is a kind of with good selectivity, easily and fast detect chromium ion method seem for the protection and monitoring of environment
It is particularly important.
The detection of traditional trivalent chromic ion is needed by large-scale instrument, majority using voltammetry, atomic absorption spectrography (AAS),
Surface plasma enhances resonance scattering and colorimetric method more concerned recently etc., although these methods can be used to detect
Trivalent chromic ion, but be restricted since equipment instrument is huge.Such as ferrous ammonium sulfate titration can be used to detect three
Valence chromium ion, but system is had a huge impact due to containing a large amount of vanadium in sample, limit the use of the method.
Common diphenyl carbazide spectrophotometry is simple with equipment, accurate, detection line is low and is widely used, but the method needs
Resolution is boiled using heating, to easily cause bumping, the volume for boiling water sample is difficult to hold, to influence the accurate of inspection
Property and sensitivity.Inductively coupled method plasmatorch is a kind of spectroscopic analysis methods of excitation light source, in conventional analysis extensively
It uses, has many advantages, such as that analysis speed is fast, precision is high, but sample needs to clear up in the analysis process, and needs by big
Type instrument, is unfavorable for real-time monitoring.And fluorescence probe method is mainly that complexing occurs for fluorescence probe substance and heavy metal ion,
By naked eyes it can be observed that the variation of color, has many advantages, such as simple, quick, high sensitivity.The China of applicant's application is specially
Benefit 201510869087.0 " the response type rhodamine fluorescence probe and its preparation and application of detection mercury ion ", in acetonitrile solution
In, it is 560nm in excitation wavelength, detection launch wavelength is 580nm, and the concentration for detecting mercury ion exists using fluorescent spectrometry
0.89-60 μM of range reach one very well it is linear, using fluorescence probe method detection mercury ion solution, it can be achieved that mercury ion
Real-time and quick detection, have preferable application prospect in terms of environment measuring.Chinese patent 201310410725.3 " utilizes
The method of the stable gold nano grain detection trivalent chromic ion of gamma-polyglutamic acid ", is added various concentration in sodium borohydride solution
Trivalent chromic ion, the stable gold nano grain of gamma-polyglutamic acid has preferable sensitivity and selectivity to trivalent chromic ion.
Rhodamine B fluorescent dye is a kind of good bioluminescence substance, has good photophysical property, is absorbed
With transmitting all at long wave (> 550nm), the advantages that fluorescence quantum yield is high, and molar extinction coefficient is big, and background interference is small, therefore
There is important application prospect in terms of developing fluorescence probe.
Summary of the invention
The object of the present invention is to provide a kind of new method of rhodamine fluorescence probe detection trivalent chromic ion, this method behaviour
Work is simple, detection is quick and high sensitivity, can be carried out the highly sensitive identification of trivalent chromic ion in solution.
In order to achieve the above object, the present invention provides a kind of rhodamine fluorescence probes in detection trivalent chromic ion content
In application.
Preferably, the structural formula of the rhodamine fluorescence probe are as follows:
The present invention also provides a kind of method using rhodamine fluorescence probe detection trivalent chromic ion, feature exists
In, comprising:
Step 1: preparing rhodamine fluorescence probe solution；
Step 2: preparing trivalent chromic ion solution；
Step 3: preparing the NaOH/NaH of pH=6.0~7.02PO4Buffer solution；
Step 4: the rhodamine fluorescence probe solution that step 1 obtains being added to the NaOH/ that step 3 obtains respectively
NaH2PO4Multiple buffer systems containing fluorescence probe are obtained in buffer solution, the step 2 for being separately added into different volumes is resulting
Trivalent chromic ion solution obtains the trivalent chromic ion solution of various concentration, stands, under conditions of excitation wavelength is 560nm, inspection
The fluorescence intensity that launch wavelength is 582nm is surveyed, using the concentration of chromium ion as abscissa, fluorescence intensity is ordinate mapping, is obtained
Linear relationship curve；
Step 5: the rhodamine fluorescence probe solution that step 1 obtains is added to the NaOH/NaH that step 3 obtains2PO4It is slow
It rushes in solution and obtains the buffer system containing fluorescence probe, trivalent chromic ion solution to be measured is added, stand, be in excitation wavelength
Under conditions of 560nm, the fluorescence intensity that detection launch wavelength is 582nm, the linear relationship curve according to obtained in step 4, meter
Calculate the concentration of chromium ion.
Preferably, the structural formula of the rhodamine fluorescence probe in the step 1 are as follows:
Preferably, the preparation method of the rhodamine fluorescence probe solution in the step 1 includes: to weigh certain mole
It is 1x10 that the rhodamine fluorescence probe of amount is configured to 100mL concentration in acetonitrile solvent-3The fluorescence probe solution of M, then takes
1mL above-mentioned concentration is 1x10-3The fluorescence probe solution of M is added in 10mL volumetric flask, then with acetonitrile solvent constant volume, shake
It is even, obtain 1x10-4The fluorescence probe solution of M, the concentration for taking 1mL above-mentioned are 1x10-4The fluorescence probe solution of M is added to 10mL
In volumetric flask, then with acetonitrile solvent constant volume, shake up, obtain 1x10-5The rhodamine fluorescence probe solution of M.
It is highly preferred that the purity of the acetonitrile solvent is 95~98wt%.
Preferably, the preparation method of the trivalent chromic ion solution in the step 2 includes: weigh certain molar weight three
It is 1x10 that valence chromium compound is configured to 100mL concentration in acetonitrile solvent-3The trivalent chromic ion solution of M, then takes 1mL above-mentioned
Concentration is 1x10-3The trivalent chromic ion solution of M is added in the volumetric flask of 10mL, then with acetonitrile solvent constant volume, shake up, obtain
Concentration is 1x10-4The trivalent chromic ion solution of M, the concentration for then taking 1mL above-mentioned are 1x10-4The trivalent chromic ion solution of M is added
Into the volumetric flask of 10mL, then with acetonitrile solvent constant volume, shake up, obtain concentration be 1x10-5The trivalent chromic ion solution of M.
It is highly preferred that the purity of the trivalent chromium compound is 95~98wt%.
Preferably, the NaOH/NaH in the step 32PO4The preparation method of buffer solution includes: to weigh sodium hydroxide
The sodium hydroxide solution for preparing 0.1mol/L, weighs sodium dihydrogen phosphate 0.68g, the sodium hydroxide solution of 0.1mol/L is added
29.1mL is diluted with water to 100mL, obtains the NaOH/NaH of pH=6.0~7.02PO4Buffer solution.
It is highly preferred that the purity of the sodium dihydrogen phosphate is 95~98wt%, the purity of the sodium hydroxide is 95
~98wt%.
Preferably, the dosage of the rhodamine fluorescence probe solution in the step 4 is 10 μ L, in the step 5
Rhodamine fluorescence probe solution dosage be 10 μ L.
Preferably, the rhodamine fluorescence probe limits up to 1.0 μM the detection of trivalent chromic ion solution.
The fluorescence probe of rhodamine of the invention is complexed in acetonitrile solution with trivalent chromic ion, and color is by colourless
Become red, is 560nm in excitation wavelength, detecting its launch wavelength is 582nm, this fluorescence probe using fluorescent spectrometry
Fluorescence intensity increased characteristic with the increase of trivalent chromic ion concentration, the highly sensitive detection of progress.In trivalent chromic ion
Concentration be 1.0-55 μM in the range of, the fluorescence intensity change value of fluorescence probe and the concentration of trivalent chromic ion are at good line
Sexual intercourse, related coefficient 0.952.
Compared with prior art, the invention has the benefit that
(1) fluorescence probe energy Selective recognition trivalent chromic ion of the present invention, and not by the interference of other common ions, glimmering
Luminous intensity is high.
(2) detection of trivalent chromic ion is carried out using fluorescence probe prepared by the present invention, detection process is simple and convenient, clever
Sensitivity is high, detection line is low, it can be achieved that the rapid sensitive to trivalent chromic ion detects.
(3) it is 7.0-11.0 that the probe, which is suitable for pH value range, this range can satisfy most biological samples
It is required that the high sensitivity detection line of the probe can reach 1.0 μM.
(4) the method for the present invention is easy to operate, detection is quick, high sensitivity and selectivity are good, and the fluorescence probe is to trivalent chromium
Ion has good selectivity, has preferable using effect in terms of environment measuring.
Detailed description of the invention
Fig. 1 is the ultraviolet variation map that fluorescence probe is added before and after trivalent chromic ion；In Fig. 1, abscissa is ultraviolet suction
It receives wavelength (nm), ordinate is absorbance.
Fig. 2 is the change in fluorescence map that fluorescence probe is added before and after trivalent chromic ion；In Fig. 2, abscissa is fluorescence hair
Ejected wave is long (nm), and ordinate is fluorescence intensity.
Fig. 3 be concentration be 10 μM in acetonitrile solution to different metal ion (Fe3+、Co2+、Ni2+、Sr2+、Ba2+、Mn2 +、Zn2+、Pb2+、Ca2+、Cd2+) selection interference detection fluorescence response figure；In Fig. 3, abscissa is different metal ion,
Ordinate is fluorescence intensity.
Fig. 4 be concentration be 10 μM in acetonitrile solution to the fluorescence spectrum response diagram of trivalent chromic ion；In Fig. 4, horizontal seat
It is designated as fluorescence emission wavelengths (nm), ordinate is fluorescence intensity.
Fig. 5 is the Job-Plot curve that concentration is 60 μM with trivalent chromic ion complexing ratio；Abscissa is c [Cr3+]/c[Cr3+
+ probe], ordinate is fluorescence F-F0, wherein F, F0It is the fluorescent emission intensity in 560nm.
Fig. 6 be concentration be 10 μM in different solvents (methanol, ethyl alcohol, acetone, acetonitrile, DMF) to the glimmering of trivalent chromic ion
Photoresponse spectrogram；Abscissa is different solvent, and ordinate is fluorescence intensity.
It is a series of that Fig. 7 is that the probe solution that concentration is 50 μM is configured with using sodium dihydrogen phosphate/sodium hydroxide buffer solution
The buffer solution of different pH, is then added a certain amount of trivalent chromic ion into probe solution, and fluorescence intensity abscissa is
Fluorescence emission wavelengths (nm), ordinate are fluorescence intensity.
Shown in Fig. 8,0 to 1000 μM of Cr is added in 10 μM of probes in acetonitrile solution3+The fluorescence emission spectrogram of compound of ion, when
It, which reaches, has good linear between 1.0 μM and 55 μM, linearly dependent coefficient reaches 0.952, and lowest detection is limited to 1.0 μM.
Abscissa is Cr3+Concentration, ordinate be probe relative intensity of fluorescence F/F0, the linear relationship curve (λ that is then madeex
=560nm).
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.The purity of acetonitrile solvent used in following embodiment is 99wt%, and the purity of sodium dihydrogen phosphate is 98wt%, institute
The purity for the sodium hydroxide stated is 98wt%.
The structural formula of rhodamine fluorescence probe in following embodiment is formula (1), and synthetic method is documented in Chinese special
Embodiment 1 in benefit 201510869087.0 " the response type rhodamine fluorescence probe and its preparation and application of detection mercury ion "
In.
Embodiment 1
(1) rhodamine fluorescence probe is dissolved in acetonitrile solvent, is made into 10 μM of fluorescence probe solution, chromic nitrate is dissolved in
In acetonitrile solvent, 10 μM of trivalent chromic ion solution are configured to, 10 μM of fluorescence probe solution of 1mL are added to 10 μM of trivalents of 1mL
In chromium ion solution, the ultraviolet variation map of fluorescence probe solution before and after trivalent chromic ion solution is added in test, as a result such as Fig. 1 institute
Show.
(2) rhodamine fluorescence probe is dissolved in acetonitrile solvent, is made into 10 μM of fluorescence probe solution, chromic nitrate is dissolved in
In acetonitrile solvent, 10 μM of trivalent chromic ion solution are configured to, 10 μM of fluorescence probe solution of 1mL are added to 10 μM of trivalents of 1mL
In chromium ion solution, fluorescence excitation and the transmitting variation map of trivalent chromic ion solution front and back fluorescence probe solution is added in test,
As a result as shown in Figure 2.
(3) rhodamine fluorescence probe is dissolved in acetonitrile solvent, 10 μM of fluorescence probe solution is made into, respectively by FeCl3、
CoCl2、NiCl2、SrCl2、BaCl2、MnCl2、ZnCl2、Pb(NO3)2、CaCl2、CdCl2It is dissolved in acetonitrile solvent, is made into 10 μM
Fe3+、Co2+、Ni2+、Sr2+、Ba2+、Mn2+、Zn2+、Pb2+、Ca2+And Cd2+Fluorescence probe is dissolved in acetonitrile by metal ion solution
In solvent, 10 μM of trivalent chromic ion solution are configured to, carry out selection interference detection, specific steps are as follows: respectively by 10 μM of 1mL
Fluorescence probe solution and 10 μM of 1mL of Fe3+、Co2+、Ni2+、Sr2+、Ba2+、Mn2+、Zn2+、Pb2+、Ca2+And Cd2+Solion is mixed
It closes, under conditions of excitation wavelength is 560nm, detects the fluorescence intensity that launch wavelength is 582nm；By 10 μM of fluorescence probes of 1mL
After solution is mixed with 10 μM of trivalent chromic ion solution of 0.5mL, then the Fe with 10 μM of 0.5mL respectively3+、Co2+、Ni2+、Sr2+、Ba2 +、Mn2+、Zn2+、Pb2+、Ca2+And Cd2+Solion mixing, under conditions of excitation wavelength is 560nm, detection launch wavelength is
The fluorescence intensity of 582nm；As a result as shown in Figure 3.
(4) theoretical based on Stern-Volmer, rhodamine fluorescence probe solution is investigated for Cr3+When ion is detected
The range of linearity and practical minimal detectable concentration.
Rhodamine fluorescence probe is dissolved in acetonitrile solvent, fluorescence probe solution is configured to, respectively by this fluorescence probe
It is dissolved in acetonitrile solvent, is configured to trivalent chromic ion solution, successively in 0 μM, 1 μM, 2 μM, 3 μM, 4 μM, 5 μM, 6 μM, 7 μM, 8 μ
M, in 9 μM and 10 μM of fluorescence probe solution by volume 1:1 be added 10 μM, 9 μM, 8 μM, 7 μM, 6 μM, 5 μM, 4 μM, 3 μM, 2 μM,
1 μM and 0 μM of trivalent chromic ion solution, by carrying out the variation of its spectrogram of fluorometric investigation, excitation wavelength 560nm, launch wavelength is
Then 582nm maps according to the maximum changing value of fluorescence intensity and makes the Job-Plot curve of complexing ratio；Abscissa is c
[Cr3+]/c[Cr3++ probe], ordinate is fluorescence F-F0, wherein F, F0It is the fluorescent emission intensity in 560nm.Fluorescence probe is molten
For liquid under the excitation of 560nm, fluorescence intensity is very weak, and with the addition of chromium ion, fluorescence intensity constantly enhances, according to
Stern-Volmer equation:
F/F0=1+KsvCq
Wherein F0It is respectively indicated with F and Cr is added3+The fluorescence intensity of rhodamine fluorescence probe measured by before and after ion, Ksv
It is enhancing constant, CqFor Cr3+Ion concentration.RHPT enhances degree and Cr3+Good linear relationship is presented in ion, such as Fig. 5 institute
Show.
(5) rhodamine fluorescence probe is dissolved in respectively methanol, ethyl alcohol, acetone, acetonitrile, in DMF solvent, be made into 10 μM it is glimmering
Light probe solution, chromic nitrate is dissolved in acetonitrile solvent, is configured to 10 μM of trivalent chromic ion solution, by 10 μM of fluorescence probes of 1mL
Solution is added in 10 μM of trivalent chromic ion solution of 1mL, excitation wavelength 560nm, launch wavelength 582nm, as a result such as Fig. 6
It is shown.
(6) rhodamine fluorescence probe is dissolved in acetonitrile solvent, is made into 50 μM of fluorescence probe solution, chromic nitrate is dissolved in
In acetonitrile solvent, be configured to 10 μM of trivalent chromic ion solution, respectively 50 μM of fluorescence probe solution of 1mL be added 1mL pH be 0,
1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.0,11.0,12.0 sodium dihydrogen phosphate/sodium hydroxide buffer is molten
Liquid, adds 10 μM of trivalent chromic ion solution of 1mL, excitation wavelength 560nm, launch wavelength 582nm, detection be added chromium from
Fluorescence intensity before and after sub- solution, as a result such as Fig. 7.
(7) rhodamine fluorescence probe is dissolved in acetonitrile solvent, is made into 50 μM of fluorescence probe solution, chromic nitrate is dissolved in
In acetonitrile solvent, it is configured to 0~100 μM of trivalent chromic ion solution, takes the rhodamine fluorescence probe of 1mL to sequentially add different dense
The trivalent chromic ion solution of degree, excitation wavelength 560nm, launch wavelength 582nm are detected glimmering before and after chromium ion solution is added
Luminous intensity, good linear when having between its 5 μM and 55 μM of arrival, linearly dependent coefficient reaches 0.981, and lowest detection is limited to
1.0 μM, as a result such as Fig. 8, opposite become occurs for the height that wherein setting of slit width can also be such that detection limits in fluorescence detection equipment
Change.
Embodiment 2
A method of trivalent chromic ion, specific steps are detected using rhodamine fluorescence probe are as follows:
Step 1: preparing rhodamine fluorescence probe solution: weighing the rhodamine fluorescence probe of certain molar weight in acetonitrile
It is 1x10 that 100mL concentration is configured in solvent-3The fluorescence probe solution of M, the concentration for then taking 1mL above-mentioned are 1x10-3M's is glimmering
Light probe solution is added in the dry volumetric flask of 10mL, then with acetonitrile solvent constant volume, shake up, obtain 1x10-4The fluorescence of M is visited
Needle solution, the concentration for taking 1mL above-mentioned are 1x10-4The fluorescence probe solution of M is added in the dry volumetric flask of 10mL, then uses second
Nitrile solvent constant volume shakes up, and obtains 1x10-5The rhodamine fluorescence probe solution of M；
Step 2: preparing trivalent chromic ion solution: weighing the trivalent chromium compound chromic nitrate of certain molar weight in acetonitrile solvent
In be configured to 100mL concentration be 1x10-3The trivalent chromic ion solution of M, the concentration for then taking 1mL above-mentioned are 1x10-3The trivalent of M
Chromium ion solution is added in the volumetric flask of the drying of 10mL, then with acetonitrile solvent constant volume, shake up, obtain concentration be 1x10-4M
Trivalent chromic ion solution, the concentration for then taking 1mL above-mentioned be 1x10-4The trivalent chromic ion solution of M is added to the drying of 10mL
Volumetric flask in, then with acetonitrile solvent constant volume, shake up, obtain concentration be 1x10-5The trivalent chromic ion solution of M；
Step 3: preparing the NaOH/NaH of pH=7.02PO4Buffer solution: the hydrogen-oxygen that sodium hydroxide prepares 0.1mol/L is weighed
Change sodium solution, weighs sodium dihydrogen phosphate 0.68g, the sodium hydroxide solution 29.1mL of 0.1mol/L is added, is diluted with water to
100mL obtains the NaOH/NaH of pH=7.02PO4Buffer solution.
Step 4: the rhodamine fluorescence probe solution 10uL that step 1 obtains being added to the NaOH/ that step 3 obtains respectively
NaH2PO4Multiple buffer systems containing fluorescence probe are obtained in buffer solution 10uL, be separately added into 0uL, 10uL, 20uL,
30uL, 40uL, 50uL, 60uL, 70uL, 80uL, the resulting trivalent chromic ion solution of step 2 of 90uL, 100uL, obtain difference
The trivalent chromic ion solution of concentration carries out constant volume using acetonitrile solution, stands 1min, under conditions of excitation wavelength is 560nm,
The fluorescence intensity that launch wavelength is 582nm is detected, using the concentration of chromium ion as abscissa, fluorescence intensity is ordinate mapping, is obtained
To linear relationship curve y=1.0597+0.02253x；
Step 5: the rhodamine fluorescence probe solution 10uL that step 1 obtains is added to the NaOH/ that step 3 obtains
NaH2PO4The buffer system containing fluorescence probe is obtained in buffer solution 10uL, and trivalent chromic ion solution 10uL to be measured is added,
1min is stood, under conditions of excitation wavelength is 560nm, the fluorescence intensity that detection launch wavelength is 582nm, according in step 4
Obtained linear relationship curve, the concentration for calculating chromium ion is 1.0x10-6M。
Embodiment 3
A method of trivalent chromic ion, specific steps are detected using rhodamine fluorescence probe are as follows:
Step 1: preparing rhodamine fluorescence probe solution: the rhodamine fluorescence probe reference
The synthetic method of 201510869087.0 " the response type rhodamine fluorescence probes and its preparation and application of detection mercury ion ".Institute
The preparation method for the rhodamine fluorescence probe solution stated are as follows: weigh the rhodamine fluorescence probe of certain molar weight in acetonitrile
It is 1x10 that 100mL concentration is configured in solvent-3The fluorescence probe solution of M, the concentration for then taking 1mL above-mentioned are 1x10-3M's is glimmering
Light probe solution is added in the dry volumetric flask of 10mL, then with acetonitrile solvent constant volume, shake up, obtain 1x10-4The fluorescence of M is visited
Needle solution, the concentration for taking 1mL above-mentioned are 1x10-4The fluorescence probe solution of M is added in the dry volumetric flask of 10mL, then uses second
Nitrile solvent constant volume shakes up, and obtains 1x10-5The rhodamine fluorescence probe solution of M；
Step 2: preparing trivalent chromic ion solution: weighing the trivalent chromium compound chromic nitrate of certain molar weight in acetonitrile solvent
In be configured to 100mL concentration be 1x10-3The trivalent chromic ion solution of M, the concentration for then taking 1mL above-mentioned are 1x10-3The trivalent of M
Chromium ion solution is added in the volumetric flask of the drying of 10mL, then with acetonitrile solvent constant volume, shake up, obtain concentration be 1x10-4M
Trivalent chromic ion solution, the concentration for then taking 1mL above-mentioned be 1x10-4The trivalent chromic ion solution of M is added to the drying of 10mL
Volumetric flask in, then with acetonitrile solvent constant volume, shake up, obtain concentration be 1x10-5The trivalent chromic ion solution of M；
Step 3: preparing the NaOH/NaH of pH=7.02PO4Buffer solution: the hydrogen-oxygen that sodium hydroxide prepares 0.1mol/L is weighed
Change sodium solution, weighs sodium dihydrogen phosphate 0.68g, the sodium hydroxide solution 29.1mL of 0.1mol/L is added, is diluted with water to
100mL obtains the NaOH/NaH of pH=7.02PO4Buffer solution.
Step 4: the rhodamine fluorescence probe solution 10uL that step 1 obtains being added to the NaOH/ that step 3 obtains respectively
NaH2PO410 buffer systems containing fluorescence probe are obtained in buffer solution 10uL, are separately added into 10,20,30,40,50,60,
The resulting trivalent chromic ion solution of the step 2 of 70,80,90,100 μ L, obtains the trivalent chromic ion solution of various concentration, uses second
Nitrile solvent carries out being settled to 2mL, stands 1min, and under conditions of excitation wavelength is 560nm, detection launch wavelength is 582-
The fluorescence intensity of 584nm, as a result as shown in Figure 4.(the small figure in Fig. 4 is that the fluorescence probe of rhodamine is added to 0~100 μM
Trivalent chromic ion in fluorescence intensity table linear diagram, and have preferable linear change at 5~55 μM.)
From fluorescence spectrum it can be seen that the fluorescence intensity of fluorescence probe increases with the increase of trivalent chromic ion concentration, to most
After tend towards stability, and the enhancement value of fluorescence intensity and trivalent chromic ion concentration have good linear relationship, R2=0.981.
The present invention utilizes fluorescence probe, carries out the highly sensitive detection of trivalent chromic ion, the fluorescence intensity change of fluorescence probe
Value and trivalent chromic ion concentration have good linear relationship, related coefficient R2=0.952, it can to the detection line of trivalent chromic ion
Reach 1.0 μM.The method of the present invention is easy to operate, high sensitivity, detection is quick and selection type is good, can be to the trivalent in mixing sample
Chromium ion carries out online rapid sensitive detection in situ.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be applied to various the field of the invention completely, for those skilled in the art, can readily implement
In addition modification, therefore under the universal defined by being required without departing substantially from claim and equivalency range, the present invention is simultaneously unlimited
In specific details and embodiment shown and described herein.
Claims (4)
1. a kind of method using rhodamine fluorescence probe detection trivalent chromic ion, which is characterized in that the rhodamine
The structural formula of fluorescence probe are as follows:
The detecting step includes:
Step 1: preparing rhodamine fluorescence probe solution, the solvent of the rhodamine fluorescence probe solution is acetonitrile；
Step 2: preparing trivalent chromic ion solution, the solvent of the trivalent chromic ion solution is acetonitrile；
Step 3: preparing the NaOH/NaH of pH=7.02PO4Buffer solution；
Step 4: the rhodamine fluorescence probe solution that step 1 obtains being added to the NaOH/NaH that step 3 obtains respectively2PO4It is slow
Rush in solution and obtain multiple buffer systems containing fluorescence probe, be separately added into the resulting trivalent chromiums of step 2 of different volumes from
Sub- solution obtains the trivalent chromic ion solution of various concentration, stands, and under conditions of excitation wavelength is 560nm, detects transmitted wave
The fluorescence intensity of a length of 582nm, using the concentration of chromium ion as abscissa, fluorescence intensity is ordinate mapping, obtains linear relationship
Curve；
Step 5: the rhodamine fluorescence probe solution that step 1 obtains is added to the NaOH/NaH that step 3 obtains2PO4It buffers molten
The buffer system containing fluorescence probe is obtained in liquid, trivalent chromic ion solution to be measured is added, and is stood, is in excitation wavelength
Under conditions of 560nm, the fluorescence intensity that detection launch wavelength is 582nm, the linear relationship curve according to obtained in step 4, meter
Calculate the concentration of chromium ion；The rhodamine fluorescence probe limits up to 1.0 μM the detection of trivalent chromic ion solution.
2. utilizing the method for rhodamine fluorescence probe detection trivalent chromic ion as described in claim 1, which is characterized in that institute
The preparation method of rhodamine fluorescence probe solution in the step 1 stated includes: the rhodamine fluorescence for weighing certain molar weight
It is 1x10 that probe is configured to 100mL concentration in acetonitrile solvent-3The fluorescence probe solution of M, the concentration for then taking 1mL above-mentioned are
1x10-3The fluorescence probe solution of M is added in 10mL volumetric flask, then with acetonitrile solvent constant volume, shake up, obtain 1x10-4M's
Fluorescence probe solution, the concentration for taking 1mL above-mentioned are 1x10-4The fluorescence probe solution of M is added in 10mL volumetric flask, then uses second
Nitrile solvent constant volume shakes up, and obtains 1x10-5The rhodamine fluorescence probe solution of M.
3. utilizing the method for rhodamine fluorescence probe detection trivalent chromic ion as described in claim 1, which is characterized in that institute
The preparation method of trivalent chromic ion solution in the step 2 stated includes: to weigh the trivalent chromium compound of certain molar weight in acetonitrile
It is 1x10 that 100mL concentration is configured in solvent-3The trivalent chromic ion solution of M, the concentration for then taking 1mL above-mentioned are 1x10-3M's
Trivalent chromic ion solution is added in the volumetric flask of 10mL, then with acetonitrile solvent constant volume, shake up, obtain concentration be 1x10-4M's
Trivalent chromic ion solution, the concentration for then taking 1mL above-mentioned are 1x10-4The trivalent chromic ion solution of M is added to the volumetric flask of 10mL
In, then with acetonitrile solvent constant volume, shake up, obtain concentration be 1x10-5The trivalent chromic ion solution of M.
4. utilizing the method for rhodamine fluorescence probe detection trivalent chromic ion as described in claim 1, which is characterized in that institute
The dosage of rhodamine fluorescence probe solution in the step 4 stated is 10 μ L, the rhodamine fluorescence probe in the step 5
The dosage of solution is 10 μ L.
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| US9023654B2 (en) * | 2011-07-25 | 2015-05-05 | Metawater Co., Ltd. | Method and apparatus for measuring bromate ions |
| CN105385439A (en) * | 2015-12-01 | 2016-03-09 | 东华大学 | Reaction type Rhodamine-class fluorescence probe for mercury ion detection and preparation as well as application thereof |
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| CN105385439A (en) * | 2015-12-01 | 2016-03-09 | 东华大学 | Reaction type Rhodamine-class fluorescence probe for mercury ion detection and preparation as well as application thereof |
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