CN105907387B - A kind of method that stannous ion is detected using rhodamine fluorescence probe - Google Patents

A kind of method that stannous ion is detected using rhodamine fluorescence probe Download PDF

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CN105907387B
CN105907387B CN201610255254.7A CN201610255254A CN105907387B CN 105907387 B CN105907387 B CN 105907387B CN 201610255254 A CN201610255254 A CN 201610255254A CN 105907387 B CN105907387 B CN 105907387B
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fluorescence probe
stannous ion
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rhodamine
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光善仪
徐曼曼
赵刚
徐洪耀
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Donghua University
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Abstract

The invention provides a kind of method that stannous ion is detected using rhodamine fluorescence probe, it is characterised in that including：Rhodamine fluorescence probe solution is added to NaOH/NaH respectively2PO4Multiple buffer systems containing fluorescence probe are obtained in cushioning liquid, it is separately added into the stannous ion solution of different volumes, obtain the stannous ion solution of various concentrations, stand, under conditions of excitation wavelength is 560nm, the fluorescence intensity that launch wavelength is 587nm is detected, using the concentration of stannous ion as abscissa, fluorescence intensity is mapped for ordinate, obtains linear relationship curve；Rhodamine fluorescence probe solution is added to NaOH/NaH2PO4The buffer system containing fluorescence probe is obtained in cushioning liquid, adds stannous ion solution to be measured, is stood, under conditions of excitation wavelength is 560nm, the fluorescence intensity that launch wavelength is 587nm is detected, calculates the concentration of stannous ion.The inventive method is simple to operate, detection is quick, high sensitivity and selectivity are good.

Description

A kind of method that stannous ion is detected using rhodamine fluorescence probe
Technical field
It is more particularly to a kind of to be examined using rhodamine fluorescence probe the invention belongs to fluorescence probe material detection method field The method for surveying stannous ion.
Background technology
Stannous ion is applied to the historical origin of pre- anti-caries for a long time, as micro member necessary to human physiological activity Element, a large amount of evidences show Sn2+Generation except can effectively suppress cancer cell, may additionally facilitate the synthesis of protein and nucleic acid, promote Body grows, and also participates in forming the biological respinse of a variety of enzymes and flavo-enzyme, so as to strengthen the stability of vivo environment. The shortage of stannous may result in undergrowth and hearing disability, but excessively accumulation causes to be metabolized interference, meeting to zinc ion stannous Influence respiratory tract and digestive system.
Stannous ion has very strong reproducibility, SnCl2It is familiar reducing agent.It can be many metal ions also Original is into low-oxidation-state, or even reverts to metal.Stannous ion also has very strong coordinating, is reported at (synthesis chemistry, 2006) 1- (2- pyridylazos) -2- naphthalenes (PAN) and stannous ion can be complexed well to be formed new mixed micelle and has good fluorescence Performance, so as to reach the purpose of detection stannous, 2ngmg can be reached using fluorescent spectrometry detection line-1。
At present, people are used for detecting Sn2+Method have flame atomic absorption spectrometry, current potential film sensing method and ultraviolet/can See AAS, compared to these methods, XRF has simple to operate, high sensitivity, the good advantage of selectivity. (Analyst, 2014,139,5223) reports design and has synthesized two kinds of Sn for being used for eucaryon and prokaryotic2+Fluorescence probe, its Detection line respectively reaches 5.7 × 10-7With 4.6 × 10-7.Applicant application Chinese patent 201510869087.0 " detection mercury from The response type rhodamine fluorescence probe of son and its preparation and application ", in acetonitrile solution, using fluorescent spectrometry, are being excited Wavelength is 560nm, and detection launch wavelength is 580nm, and the concentration for detecting mercury ion reaches one very well in 0.89-60 μM of scope It is linear, mercury ion solution is detected using fluorescence probe method, the real-time and quick detection to mercury ion can be achieved, is examined in environment There is preferable application prospect in terms of survey.
The fluorescence probe of rhodamine and its derivative as ON/OFF form, there is higher fluorescence quantum yield, it is larger Molar extinction coefficient, there is longer transmitting and absorbing wavelength in visible region.Helical form rhodamine lactam compound is in itself With certain structural tension, after being combined with heavy metal particles, the protonation of lactams nitrogen-atoms will cause nitrogen-atoms electric charge Density is reduced, so as to trigger the cracking of spiral center C-N keys, meanwhile, the helical ring of script electron rich will carry out electric charge after scission of link Reset, the big pi bond structure of more stable rigid plane is formed, so as to produce change in fluorescence and color change.And different metal ions After effect, the effect formed is different, and fluorescence can occur for Rhodamine Derivatives and the change of color is also different.Thus Luo Dan Bright and its derivative has very big development prospect as probe in detecting heavy metal ions.Fluorescent molecular probe has spirit Sensitivity is high, and selectivity is strong, not damaged quick and precisely the features such as in detection organism connection metal show the advantage of uniqueness, And it is widely used in the biological study (Inorg.Chim.Acta, 2012,381,2-14) of metal ion participation.Rhodamine B is again Claim rose red b, rhodamine base fluorescent probe has good fluorescence property and less cytotoxicity, is widely used in organism The detection of interior ion and small molecule, the analysis and detection of large biological molecule and the research of complex biological system.Such fluorescence is visited Enhanced response from scratch is presented in pin fluorescence before and after identification, has very high sensitivity, passes through the essence to recognition group The heart selects and designs such probe and show good selectivity and anti-interference (Chem.Rev.2012.112.1910- 1956).Regrettable is the report for seldom seeing at present the rhodamine base fluorescent probe for being identification stannous ion.In summary, It has developed bioactivity and pharmacology of a kind of rhodamine base fluorescent probe of detectable stannous ion for research stannous ion Effect has important application prospect.
The content of the invention
It is an object of the invention to provide a kind of method that stannous ion is detected using rhodamine fluorescence probe.
In order to achieve the above object, the invention provides a kind of rhodamine fluorescence probe in stannous ion content is detected Application.
Preferably, the structural formula of described rhodamine fluorescence probe is：
Present invention also offers a kind of method that stannous ion is detected using rhodamine fluorescence probe, it is characterised in that Including：
Step 1：Prepare rhodamine fluorescence probe solution；
Step 2：Prepare stannous ion solution；
Step 3：Prepare the NaOH/NaH of pH=6.0~7.02PO4Cushioning liquid；
Step 4：The rhodamine fluorescence probe solution that step 1 obtains is added to the NaOH/ that step 3 obtains respectively NaH2PO4Multiple buffer systems containing fluorescence probe are obtained in cushioning liquid, are separately added into obtained by the step 2 of different volumes Stannous ion solution, the stannous ion solution of various concentrations is obtained, stood, under conditions of excitation wavelength is 560nm, detection hair The a length of 587nm of ejected wave fluorescence intensity, using the concentration of stannous ion as abscissa, fluorescence intensity is mapped for ordinate, obtains line Sexual intercourse curve；
Step 5：The rhodamine fluorescence probe solution that step 1 obtains is added to the NaOH/NaH that step 3 obtains2PO4It is slow Rush in solution and obtain the buffer system containing fluorescence probe, add stannous ion solution to be measured, stand, be in excitation wavelength Under conditions of 560nm, detection launch wavelength is 587nm fluorescence intensity, according to the linear relationship curve obtained in step 4, is counted Calculate the concentration of stannous ion.
Preferably, the structural formula of the rhodamine fluorescence probe in described step 1 is：
Preferably, the compound method of the rhodamine fluorescence probe solution in described step 1 includes：Weigh certain mole It is 1x10 that the rhodamine fluorescence probe of amount is configured to 100mL concentration in acetonitrile solvent-3M fluorescence probe solution, Ran Houqu Concentration above-mentioned 1mL is 1x10-3M fluorescence probe solution is added in 10mL volumetric flasks, then with acetonitrile solvent constant volume, shake It is even, obtain 1x10-4M fluorescence probe solution, it is 1x10 to take the above-mentioned concentration of 1mL-4M fluorescence probe solution is added to 10mL In volumetric flask, then with acetonitrile solvent constant volume, shake up, obtain 1x10-5M rhodamine fluorescence probe solution.
It is highly preferred that the purity of described acetonitrile solvent is 95~98wt%.
Preferably, the compound method of the stannous ion solution in described step 2 includes：Weigh the stannous of certain molar weight It is 1x10 that compound is configured to 100mL concentration in acetonitrile solvent-3M stannous ion solution, the concentration for then taking 1mL above-mentioned are 1x10-3M stannous ion solution is added in 10mL volumetric flask, then with acetonitrile solvent constant volume, shake up, obtaining concentration is 1x10-4M stannous ion solution, it is 1x10 then to take the above-mentioned concentration of 1mL-4M stannous ion solution is added to 10mL appearance In measuring bottle, then with acetonitrile solvent constant volume, shake up, it is 1x10 to obtain concentration-5M stannous ion solution.
It is highly preferred that the purity of described stannous compound is 95~98wt%.
Preferably, the NaOH/NaH in described step 32PO4The compound method of cushioning liquid includes：Weigh sodium hydroxide 0.1mol/L sodium hydroxide solution is prepared, sodium dihydrogen phosphate 0.68g is weighed, adds 0.1mol/L sodium hydroxide solution 29.1mL, 100mL is diluted with water to, obtains the NaOH/NaH of pH=6.0~7.02PO4Cushioning liquid.
It is highly preferred that the purity of described sodium dihydrogen phosphate is 95~98wt%, the purity of described sodium hydroxide is 95 ~98wt%.
Preferably, the dosage of the rhodamine fluorescence probe solution in described step 4 is 10 μ L, in described step 5 The dosage of rhodamine fluorescence probe solution be 10 μ L.
Preferably, described rhodamine fluorescence probe to the test limit of stannous ion solution up to 1.0 μM.
The fluorescence probe of the present invention is complexed in acetonitrile solution with stannous ion, and color becomes pink by colourless, Be 560nm in excitation wavelength using fluorescent spectrometry, it is 587nm to detect its launch wavelength, the fluorescence intensity of this fluorescence probe with The increase of stannous ion concentration and increased characteristic, the high-sensitivity detection of progress.It is 1.2-6.2 in the concentration of stannous ion In the range of μM, the fluorescence intensity change value of fluorescence probe and the concentration of stannous ion are into good linear relationship, coefficient correlation For 0.993, lowest detection line is 0.1 μM, and the inventive method is simple to operate, detection is quick, high sensitivity and selectively good, and this is glimmering Light probe has good selectivity to stannous ion, has preferable using effect in terms of environment measuring.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) fluorescence probe energy Selective recognition stannous ion of the present invention, and do not disturbed by other common ions, fluorescence Intensity is high, fluorescence intensity is high.
(2) probe is 7.0-11.0 suitable for pH value range, and this scope can meet most biological samples It is required that the high sensitivity detection line of the probe can reach 0.1 μM.
(3) detection of stannous ion is carried out using the fluorescence probe prepared by the present invention, detection process is simple and convenient, sensitive Degree is high, detection line is low, can be achieved to detect the rapid sensitive of stannous ion.
Brief description of the drawings
Fig. 1 is the ultraviolet change collection of illustrative plates that fluorescence probe is added before and after stannous ion；In Fig. 1, abscissa is UV absorption Wavelength (nm), ordinate are absorbance.
Fig. 2 is the change in fluorescence collection of illustrative plates that fluorescence probe is added before and after stannous ion；In fig. 2, abscissa is fluorescent emission Wavelength (nm), ordinate are fluorescence intensity.(what Fig. 2 illustrations represented is change in fluorescence that fluorescence probe does not add stannous ion Spectrogram, illustrates variation in emission wavelength after addition stannous ion, and fluorescence intensity is also changed.)
Fig. 3 be concentration be 10 μM in acetonitrile solution to the fluorescence spectrum response diagram of stannous ion；In figure 3, abscissa For fluorescence emission wavelengths (nm), ordinate is fluorescence intensity.
Fig. 4 be (concentration is 10 μM) in acetonitrile solution to different metal ion (Sn2+、Fe3+、Co2+、Ni2+、Sr2+、 Ba2+、Mn2+、Zn2+、Pb2+、Ca2+、Cd2+) selection interference detection fluorescence response figure；In Fig. 4, abscissa is different gold Belong to ion, ordinate is fluorescence intensity.
Fig. 5 is the Job-Plot curves that fluorescence probe solution is complexed ratio with stannous ion；Abscissa is c [Sn2+]/c[Sn2+ + 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, ethanol, acetone, acetonitrile, DMF) to the fluorescence of stannous ion Respond 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 Different pH cushioning liquid, then adds a certain amount of stannous ion into probe solution, and fluorescence intensity abscissa is glimmering Light launch wavelength (nm), ordinate are fluorescence intensity.
Shown in Fig. 8,10 μM of probes add 0 to 15 μM of Sn in acetonitrile solution2+The fluorescence emission spectrogram of compound of ion, when it Reaching has good linear between 1.2 μM -6.2 μM, linearly dependent coefficient reaches 0.993, and its lowest detection is limited to 0.12 μM.It is horizontal Coordinate is Sn2+Concentration, ordinate be probe relative intensity of fluorescence F/F0, then made linear relationship curve (λex= 560nm)。
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.The purity of acetonitrile solvent used is 99wt% in following embodiment, and the purity of sodium dihydrogen phosphate is 98wt%, institute The purity for the sodium hydroxide stated is 98wt%, and the purity of stannous compound is 98wt%.
The structural formula of rhodamine fluorescence probe in following examples is formula (1), and its synthetic method is documented in Chinese special Embodiment 1 in profit 201510869087.0 " the response type rhodamine fluorescence probe of detection mercury ion and its preparation and application " In.
Embodiment 1
(1) rhodamine fluorescence probe is dissolved in acetonitrile solvent, is made into 10 μM of fluorescence probe solution, by stannous chemical combination Thing is dissolved in acetonitrile solvent, is configured to 10 μM of stannous ion solutions, and 10 μM of fluorescence probe solution of 1.0mL are added into 1.0mL In 10 μM of stannous ion solutions, test adds the ultraviolet change collection of illustrative plates of fluorescence probe solution before and after stannous ion solution, as a result such as Shown in Fig. 1.
(2) rhodamine fluorescence probe is dissolved in acetonitrile solvent, is made into 10 μM of fluorescence probe solution, by stannous chemical combination Thing is dissolved in acetonitrile solvent, is configured to 10 μM of stannous ion solutions, and 10 μM of fluorescence probe solution of 1.0mL are added into 1.0mL In 10 μM of stannous ion solutions, test adds the change in fluorescence collection of illustrative plates of fluorescence probe solution before and after stannous ion solution, as a result such as Shown in Fig. 2.
(3) it is theoretical based on Stern-Volmer, rhodamine fluorescence probe solution has been investigated for Sn2+Ion is detected When the range of linearity and actual minimal detectable concentration.
Rhodamine fluorescence probe is dissolved in acetonitrile solvent, is configured to fluorescence probe solution, respectively by stannous chemical combination Thing is dissolved in acetonitrile solvent, is configured to stannous ion solution, successively in 0 μM, 1 μM, 2 μM, 3 μM, 4 μM, 5 μM, 6 μM, 7 μM, 8 μ M, by volume 1 in 9 μM and 10 μM of fluorescence probe solution：1 add 10 μM, 9 μM, 8 μM, 7 μM, 6 μM, 5 μM, 4 μM, 3 μM, 2 μM, 1 μM and 0 μM of stannous ion solution, by carrying out fluorometric investigation its spectrogram change, excitation wavelength 560nm, launch wavelength is 587nm, the Job-Plot curves for being complexed ratio of then being mapped and made according to the maximum changing value of fluorescence intensity；Abscissa is c [Sn2+]/c[Sn2++ probe], ordinate is fluorescence F-F0, wherein F, F0It is the fluorescent emission intensity in 560nm.Rhodamine is glimmering For light probe under 560nm excitation, fluorescence intensity is very weak, and with the addition of stannous ion, fluorescence intensity constantly strengthens, According to Stern-Volmer equations：
F/F0=1+KsvCq
Wherein F0Represent to add Sn respectively with F2+Front and rear measured RHPT fluorescence intensity, KsvIt is to strengthen constant, CqFor Sn2+Concentration.RHPT strengthens degree and Sn2+Good linear relationship is presented, as shown in figure 5, by calculating its linear regression side Journey, linearly dependent coefficient 0.993, the range of linearity are 1.2 μM -6.2 μM, and the minimum of probe in detecting is limited to 0.1 μM.Such as Fig. 8 institutes Show.
(4) rhodamine fluorescence probe is dissolved in methanol, ethanol, acetone, acetonitrile, DMF solvent respectively, be made into 10 μM it is glimmering Light probe solution, stannous chloride is dissolved in acetonitrile solvent, is configured to 10 μM of stannous ion solutions, and 10 μM of fluorescence of 1.0mL are visited Pin solution is added in 10 μM of stannous ion solutions of 1.0mL, excitation wavelength 560nm, launch wavelength 587nm, as a result as schemed Shown in 6.
Embodiment 2
A kind of method that stannous ion is detected using rhodamine fluorescence probe, is concretely comprised the following steps：
Step 1：Prepare rhodamine fluorescence probe solution：Described rhodamine fluorescence probe reference The synthetic method of 201510869087.0 " the response type rhodamine fluorescence probe of detection mercury ion and its preparation and application ".Institute The compound method for the rhodamine fluorescence probe solution stated is：The rhodamine fluorescence probe of certain molar weight is weighed in acetonitrile It is 1x10 that 100mL concentration is configured in solvent-3M fluorescence probe solution, it is 1x10 then to take the above-mentioned concentration of 1mL-3M's is glimmering Light probe solution be added to 10mL drying volumetric flask in, then with acetonitrile solvent constant volume, shake up, obtain 1x10-4M fluorescence is visited Pin solution, it is 1x10 to take the above-mentioned concentration of 1mL-4M fluorescence probe solution is added in the volumetric flask of 10mL dryings, then uses second Nitrile solvent constant volume, shake up, obtain 1x10-5M rhodamine fluorescence probe solution；
Step 2：Prepare stannous ion solution：Weigh the stannous compound (SnCl of certain molar weight2) in acetonitrile solvent It is 1x10 to be configured to 100mL concentration-3M stannous ion solution, it is 1x10 then to take the above-mentioned concentration of 1mL-3M stannous ion Solution is added in the volumetric flask of 10mL drying, then with acetonitrile solvent constant volume, shake up, it is 1x10 to obtain concentration-4M stannous Solion, it is 1x10 then to take the above-mentioned concentration of 1mL-4M stannous ion solution is added in the volumetric flask of 10mL drying, Then with acetonitrile solvent constant volume, shake up, it is 1x10 to obtain concentration-5M stannous ion solution；
Step 3：Prepare pH=7.0 NaOH/NaH2PO4Cushioning liquid：Weigh the hydrogen-oxygen that sodium hydroxide prepares 0.1mol/L Change sodium solution, weigh sodium dihydrogen phosphate 0.68g, add 0.1mol/L sodium hydroxide solution 29.1mL, be diluted with water to 100mL, obtain pH=7.0 NaOH/NaH2PO4Cushioning liquid.
Step 4：The rhodamine fluorescence probe solution 10uL that step 1 obtains is added to the NaOH/ that step 3 obtains respectively NaH2PO4Multiple buffer systems containing fluorescence probe are obtained in cushioning liquid 10uL, be separately added into 0uL, 10uL, 20uL, Stannous ion solution obtained by 30uL, 40uL step 2, obtains the stannous ion solution of various concentrations, acetonitrile solution is settled to 2mL, stand 1min, excitation wavelength be 560nm under conditions of, detection launch wavelength be 587nm fluorescence intensity, with stannous from The concentration of son is abscissa, and fluorescence intensity is mapped for ordinate, obtains linear relationship curve y=21.58+4.50225x；
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 cushioning liquid 10uL, adds stannous ion solution 10uL to be measured, it is quiet 1min is put, under conditions of excitation wavelength is 560nm, detection launch wavelength is 587nm fluorescence intensity, is obtained according in step 4 The linear relationship curve arrived, the concentration for calculating stannous ion are 2x10-6M。
Embodiment 3
Step 1：Prepare rhodamine fluorescence probe solution：Described rhodamine fluorescence probe reference The synthetic method of 201510869087.0 " the response type rhodamine fluorescence probe of detection mercury ion and its preparation and application ".Institute The compound method for the rhodamine fluorescence probe solution stated is：The rhodamine fluorescence probe of certain molar weight is weighed in acetonitrile It is 1x10 that 100mL concentration is configured in solvent-3M fluorescence probe solution, it is 1x10 then to take the above-mentioned concentration of 1mL-3M's is glimmering Light probe solution be added to 10mL drying volumetric flask in, then with acetonitrile solvent constant volume, shake up, obtain 1x10-4M fluorescence is visited Pin solution, it is 1x10 to take the above-mentioned concentration of 1mL-4M fluorescence probe solution is added in the volumetric flask of 10mL dryings, then uses second Nitrile solvent constant volume, shake up, obtain 1x10-5M rhodamine fluorescence probe solution；
Step 2：Prepare stannous ion solution：Weigh the stannous compound (SnCl of certain molar weight2) in acetonitrile solvent It is 1x10 to be configured to 100mL concentration-3M stannous ion solution, it is 1x10 then to take the above-mentioned concentration of 1mL-3M stannous ion Solution is added in the volumetric flask of 10mL drying, then with acetonitrile solvent constant volume, shake up, it is 1x10 to obtain concentration-4M stannous Solion, it is 1x10 then to take the above-mentioned concentration of 1mL-4M stannous ion solution is added in the volumetric flask of 10mL drying, Then with acetonitrile solvent constant volume, shake up, it is 1x10 to obtain concentration-5M stannous ion solution；
Step 3：Prepare pH=7.0 NaOH/NaH2PO4Cushioning liquid：Weigh the hydrogen-oxygen that sodium hydroxide prepares 0.1mol/L Change sodium solution, weigh sodium dihydrogen phosphate 0.68g, add 0.1mol/L sodium hydroxide solution 29.1mL, be diluted with water to 100mL, obtain pH=7.0 NaOH/NaH2PO4Cushioning liquid.
Step 4：The rhodamine fluorescence probe solution 10uL that step 1 obtains is added to the NaOH/ that step 3 obtains respectively NaH2PO49 buffer systems containing fluorescence probe are obtained in cushioning liquid 10uL, are separately added into 10,20,30,40,50,60, Stannous ion solution obtained by 70,80,90 μ L step 2, obtains the stannous ion solution of various concentrations, acetonitrile solution constant volume, 1min is stood, under conditions of excitation wavelength is 560nm, the fluorescence intensity that launch wavelength is 587nm is detected, with stannous ion Concentration is abscissa, and fluorescence intensity is mapped for ordinate, and it is as shown in Figure 3 to obtain linear relationship curve.
The fluorescence intensity that can learn fluorescence probe from fluorescence spectrum increases with the increase of stannous ion concentration, to the end Tend towards stability, and the enhancement value of fluorescence intensity has good linear relationship, R with stannous ion concentration2=0.993.
The present invention utilizes fluorescence probe, carries out the highly sensitive detection of stannous ion, the fluorescence intensity change value of fluorescence probe There are good linear relationship, coefficient correlation R with stannous ion concentration2=0.993, the detection line of stannous ion can reach 0.1μM.The inventive method is simple to operate, high sensitivity, detection is quick and selection type is good, can be to the stannous ion in biased sample Carry out online rapid sensitive detection in situ.
Embodiment 4
Each metal ion species are to RHPT+Sn2+The interference experiment of fluorescence probe：
Step 1：Prepare rhodamine fluorescence probe solution：Described rhodamine fluorescence probe reference The synthetic method of 201510869087.0 " the response type rhodamine fluorescence probe of detection mercury ion and its preparation and application ".Institute The compound method for the rhodamine fluorescence probe solution stated is：The rhodamine fluorescence probe of certain molar weight is weighed in acetonitrile It is 1x10 that 100mL concentration is configured in solvent-3M fluorescence probe solution, it is 1x10 then to take the above-mentioned concentration of 1mL-3M's is glimmering Light probe solution be added to 10mL drying volumetric flask in, then with acetonitrile solvent constant volume, shake up, obtain 1x10-4M fluorescence is visited Pin solution, it is 1x10 to take the above-mentioned concentration of 1mL-4M fluorescence probe solution is added in the volumetric flask of 10mL dryings, then uses second Nitrile solvent constant volume, shake up, obtain 1x10-5M rhodamine fluorescence probe solution；
Step 2：Multicomponent metal ion solution is prepared respectively, and compound method is：Weigh the metallic compound of certain molar weight (SnCl2) 100mL concentration is configured in acetonitrile solvent is 1x10-3M metal ion solution, then take the above-mentioned concentration of 1mL For 1x10-3M metal ion solution is added in the volumetric flask of 10mL drying, then with acetonitrile solvent constant volume, shake up, obtain Concentration is 1x10-4M metal ion solution, it is 1x10 then to take the above-mentioned concentration of 1mL-4M metal ion solution is added to In the volumetric flask of 10mL drying, then with acetonitrile solvent constant volume, shake up, it is 1x10 to obtain concentration-5M metal ion solution； Described metal ion is (Sn2+、Fe3+、Co2+、Ni2+、Sr2+、Ba2+、Mn2+、Zn2+、Pb2+、Ca2+、Cd2+), corresponding metal Compound is (SnCl2、FeCl3、CoCl2、NiNO3、SrCl2、BaCl2、MnCl2、ZnCl2、KCl、NaCl、Pd(NO3)2、Ca (NO3)2、CdCl2)。
Step 3：1mL metal ion solution and 1mL rhodamine fluorescence are added in 1cm quartz colorimetric utensil respectively Probe solution；Under conditions of excitation wavelength is 560nm, the fluorescence intensity that launch wavelength is 587nm is detected, fluorescence during test The greatest measure of intensity records the disturbed condition for more various ions of being mapped, only Co2+、Ni2+And Cd2+Ion Stannous ion has a slight interference effect, other metal ions substantially on influence is not interfered with stannous ion.
Step 4：Black bar as corresponding to Fig. 4, take fluorescence probe solution and then add equal dense that concentration is 10 μM The stannous ion of degree and other metal ions, then can be seen that Co by fluorescence spectrum2+、Ni2+And Cd2+The stannous of ion Ion has a slight interference effect, other metal ions substantially on influence is not interfered with stannous ion.
Embodiment 5
Step 1：Prepare rhodamine fluorescence probe solution：Described rhodamine fluorescence probe reference The synthetic method of 201510869087.0 " the response type rhodamine fluorescence probe of detection mercury ion and its preparation and application ".Institute The compound method for the rhodamine fluorescence probe solution stated is：The rhodamine fluorescence probe of certain molar weight is weighed in acetonitrile The fluorescence probe solution that concentration is 10 μM is configured in solvent；
Step 2：Prepare pH=7.0 NaOH/NaH2PO4Cushioning liquid：Weigh the hydrogen-oxygen that sodium hydroxide prepares 0.1mol/L Change sodium solution, weigh sodium dihydrogen phosphate 0.68g, add 0.1mol/L sodium hydroxide solution 29.1mL, be diluted with water to 100mL, obtain pH=7.0 NaOH/NaH2PO4Cushioning liquid.
Step 3：Prepare stannous ion solution：The stannous compound (SnCl2) of certain molar weight is weighed in acetonitrile solvent It is 1x10 to be configured to 100mL concentration-3M stannous ion solution, it is 1x10 then to take the above-mentioned concentration of 1mL-3M stannous ion Solution is added in the volumetric flask of 10mL drying, then with acetonitrile solvent constant volume, shake up, it is 1x10 to obtain concentration-4M stannous Solion；
Step 4：Add what step 2 obtained in the fluorescence probe solution that the concentration obtained in step 1 respectively is 10 μM NaOH/NaH2PO4Cushioning liquid, obtain it is a series of it is different (pH=1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0, 10.0th, 11.0,12.0) pH cushioning liquid；Take respectively 0.5mL volumes cushioning liquid add 0.5mL volumes concentration be 1x10-4M stannous ion solution, be 560nm in excitation wavelength, under conditions of launch wavelength is 587nm, detection add stannous from Fluorescence intensity before and after sub- solution, obtain the change of probe solution fluorescence intensity under condition of different pH.It was found that in pH=1.0-3.0 When fluorescence intensity be decreased obviously, pH=4.0-12.0 fluorescence intensity change unobvious, probe solution is more stable, thus should Fluorescence probe below pH=1.0-3.0 in acetonitrile solvent is influenceed bigger by acid condition, and pH is from 10.0-12.0, fluorescence Intensity has gradual enhancing, it may be possible to because fluorescence intensity has gradual enhancing, it may be possible to because with the enhancing of dihydrogen phosphate, increases Electrolyte concentration in strong solution, it is favourable to the opening of snail ring, see accompanying drawing 7.

Claims (5)

  1. A kind of 1. method that stannous ion is detected using rhodamine fluorescence probe, it is characterised in that including：
    Step 1：Prepare rhodamine fluorescence probe solution；The structural formula of described rhodamine fluorescence probe is：
    （I）；
    Step 2：Prepare stannous ion solution；
    Step 3：Prepare the NaOH/NaH of pH=6.0~7.02PO4Cushioning liquid；
    Step 4：The rhodamine fluorescence probe solution that step 1 obtains is 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 stannous ion obtained by the step 2 of different volumes Solution, the stannous ion solution of various concentrations is obtained, stood, under conditions of excitation wavelength is 560 nm, detect launch wavelength For 587 nm fluorescence intensity, using the concentration of stannous ion as abscissa, fluorescence intensity is mapped for ordinate, obtains linear relationship Curve；
    Step 5：The rhodamine fluorescence probe solution that step 1 obtains is added to the NaOH/NaH that step 3 obtains2PO4Buffer molten The buffer system containing fluorescence probe is obtained in liquid, adds stannous ion solution to be measured, stands, is 560 nm in excitation wavelength Under conditions of, detection launch wavelength is 587 nm fluorescence intensity, according to the linear relationship curve obtained in step 4, is calculated sub- The concentration of tin ion；Stannous ion concentration be 1.2-6.2 μM in the range of, the fluorescence intensity change value of fluorescence probe with The concentration of stannous ion is limited to 0.1 μM into good linear relationship, coefficient correlation 0.993, lowest detection.
  2. 2. the method for rhodamine fluorescence probe detection stannous ion is utilized as claimed in claim 1, it is characterised in that described Step 1 in the compound method of rhodamine fluorescence probe solution include：The rhodamine fluorescence for weighing certain molar weight is visited It is 1x10 that pin is configured to 100 mL concentration in acetonitrile solvent-3 M fluorescence probe solution, the concentration for then taking 1 mL above-mentioned are 1x10-3M fluorescence probe solution is added in 10 mL volumetric flasks, then with acetonitrile solvent constant volume, shake up, obtain 1x10-4 M Fluorescence probe solution, it is 1x10 to take the above-mentioned concentration of 1 mL-4M fluorescence probe solution is added in 10 mL volumetric flasks, so Afterwards with acetonitrile solvent constant volume, shake up, obtain 1x10-5M rhodamine fluorescence probe solution.
  3. 3. the method for rhodamine fluorescence probe detection stannous ion is utilized as claimed in claim 1, it is characterised in that described Step 2 in the compound method of stannous ion solution include：The stannous compound of certain molar weight is weighed in acetonitrile solvent It is 1x10 to be configured to 100 mL concentration-3M stannous ion solution, it is 1x10 then to take the above-mentioned concentration of 1 mL-3M stannous Solion is added in 10 mL volumetric flask, then with acetonitrile solvent constant volume, shake up, it is 1x10 to obtain concentration-4 M stannous Solion, it is 1x10 then to take the above-mentioned concentration of 1 mL-4M stannous ion solution is added in 10 mL volumetric flask, so Afterwards with acetonitrile solvent constant volume, shake up, it is 1x10 to obtain concentration-5M stannous ion solution.
  4. 4. the method for rhodamine fluorescence probe detection stannous ion is utilized as claimed in claim 1, it is characterised in that described Step 3 in NaOH/NaH2PO4The compound method of cushioning liquid includes：Weigh the hydrogen-oxygen that sodium hydroxide prepares 0.1 mol/L Change sodium solution, weigh the g of sodium dihydrogen phosphate 0.68, add the 0.1 mol/L mL of sodium hydroxide solution 29.1, be diluted with water to 100 mL, obtain the NaOH/NaH of pH=6.0~7.02PO4Cushioning liquid.
  5. 5. the method for rhodamine fluorescence probe detection stannous ion is utilized as claimed in claim 1, it is characterised in that described Step 4 in the dosage of rhodamine fluorescence probe solution be 10 μ L, the rhodamine fluorescence probe in described step 5 The dosage of solution is 10 μ L.
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