CN109096297A - Detect the binary channels rhodamine fluorescence probe and its application of aluminium ion and calcium ion - Google Patents
Detect the binary channels rhodamine fluorescence probe and its application of aluminium ion and calcium ion Download PDFInfo
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Abstract
The present invention provides a kind of binary channels rhodamine fluorescence probe and its application for detecting aluminium ion and calcium ion, the structural formulas of probe are as follows:
Description
Technical field
The present invention relates to the detection technique field of metal ion, in particular to a kind of bilateral for detecting aluminium ion and calcium ion
Road rhodamine fluorescence probe and its application.
Background technique
In recent years, the very big concern of academia is caused for the detection of metal ion.Because they are not only ring
Important pollutant in the pollution of border, more takes part in various basic bioprocess in organism, such as Al therein3+Content mistake
Great influence can be all caused when high or too low to human body and its environment.Al3+It is the highest metallic element of content in soil, according to
Studies have shown that the whole world acid soil 40% all because aluminium ion pollute, inhibit the growth and development of plant, and it is extremely strong
Toxicity can lead to senile dementia, memory loss and DOMS etc., but it is also widely used in production and living simultaneously,
Such as packaging material, food additives.And calcium be even more human body and life in essential metallic element, the bone of animal,
Clam shell, eggshell all contain calcium.It can also be used in reducing agent, iron and the ferroalloy of the deoxidier of alloy, the dehydrating agent of oils, metallurgy
Desulfurization and decarburizer and electron tube in getter etc..Its compound industrially, in architectural engineering and is pharmaceutically used
Way is very big.
The analysis method of common at present detection aluminium ion and calcium ion includes Optical Analysis Method, volumetric analysis, ion
Chromatography etc..In these numerous detection methods, fluorescence probe is formed due to its peculiar advantage as researcher's concern
Focus.However, there are still some problems for the fluorescence probe reported at present, including synthesis is complicated, not good enough the, response speed of selectivity
The disadvantages of not fast enough, excessively single to the selection of metal ion, so developing new binary channels fluorescence probe becomes urgent need
The new issue of solution.
Rhodamine is widely used as fluorescence probe and sensor, has high-selenium corn system in the visible region of electromagnetic spectrum
Several, extensive fluorescence, high fluorescence quantum yield and photostability pass through the carbonyl in activation spirolactone or spirolactams part
With complexing of metal ion.In general, the spirolactams formation of Rhodamine Derivatives is non-fluorescence, and the amide system meeting of its open loop
Generate the color change and strong fluorescent emission of pink.Schiff bases fluorescence probe not only synthesize it is relatively easy, but also can
With with big conjugation group and good photostability, N atom has a pair of of lone pair electrons to seek in-C=N- structure
Produced the chemical environment of an electron rich, can preferably with metallic ion coordination.Furthermore it is also possible to introduce electron rich atom
(O, N, S) is that schiff bases fluorescence probe and metallic ion coordination create more favorable electron rich chemical environment, forms new Schiff
Alkali derivant and can have preferable ion selectivity, the complex compound of formation is also very from different metallic ion coordinations
Stablize, fluorescence property is excellent.
Chinese patent 201710816511.4 " one kind is for detecting aluminium ion fluorescence probe, preparation method and application ", will
2- (5- alkyl -4- aldehyde radical -2- hydroxy phenyl) benzothiazole and 2- thenoyl hydrazine reaction prepare fluorescence probe, detect aluminium ion
Has the characteristics that highly selective, highly sensitive and good water solubility, but it has reaction complexity, cannot detect different kinds of ions simultaneously
The shortcomings that.Chinese patent 201610405043.7 " aluminium ion fluorescence probe ", passes through 2- hydroxyl-1-naphthalene Formaldehyde and o-aminophenol
Reaction condensation forms schiff base compound.The fluorescence probe itself has good chemistry, optical stability, has to aluminium ion
The specificly-response of fluorescence enhancement not by the interference of other ions, and responds rapid.201110051293.2 " Yin of Chinese patent
Diindyl class calcium ion fluorescent and its preparation method and application ", using 4- methyl o-nitrophenol as raw material, with the bromo- 2- chloroethene of 1-
Substitution reaction occurs for alkane, then reacts with 2- nitro -5- methylphenol, restores later by iron, and methyl bromoacetate replaces,
Vismeier reacts to obtain target product, and Ben Fayin increases double bond in chromophore, and conjugation increases, excitation wavelength red shift,
At or approximately at visible region, use process reduces damage of the ultraviolet light to cell, facilitates look at and detects.
Summary of the invention
The technical problem to be solved in the present invention is to provide one kind can identify aluminium ion and calcium ion fluorescence probe and its
Using.
In order to solve the above-mentioned technical problem, the technical solution of the present invention is to provide pairs of a kind of detection aluminium ion and calcium ion
Channel rhodamine fluorescence probe, which is characterized in that the structural formula of the binary channels rhodamine fluorescence probe RhBr are as follows:
The present invention also provides the binary channels rhodamine fluorescence probes of a kind of above-mentioned detection aluminium ion and calcium ion
Application method, which is characterized in that step are as follows:
Step 1: preparing the binary channels rhodamine fluorescence probe solution of detection aluminium ion and calcium ion；
Step 2: preparing aluminium ion stock solution and calcium ion stock solution；
Step 3: taking binary channels rhodamine fluorescence probe solution prepared by step 1, be separately added into prepared by step 2
The aluminium ion stock solutions of different volumes, in calcium ion stock solution, obtain aluminium ion solution, the ionic calcium soln of various concentration,
It stands；
Under conditions of fluorescence emission wavelengths 576nm, using aluminium ion concentration as abscissa, relative intensity of fluorescence is ordinate
Mapping, obtains RhBr-Al3+Linear relationship curve；Under conditions of fluorescence emission wavelengths 492nm, with calcium ion concentration for horizontal seat
Mark, relative intensity of fluorescence are ordinate mapping, obtain RhBr-Ca2+Linear relationship curve；
Step 4: by rhodamine fluorescence probe solution addition aluminium ion solution to be measured, ionic calcium soln, standing；?
Under conditions of fluorescence emission wavelengths 576nm, the RhBr-Al according to obtained in step 33+Linear relationship curve calculates aluminium to be measured
Aluminum ions concentration in solion；Under conditions of fluorescence emission wavelengths 492nm, the RhBr-Ca according to obtained in step 32+
Linear relationship curve calculates the concentration of calcium ion in ionic calcium soln to be measured.
Preferably, in the step 1, the configuration method of binary channels rhodamine fluorescence probe solution includes the following steps:
Step 1.1: weighing the binary channels rhodamine fluorescence probe of certain molar weight, to be configured to 100mL in a solvent dense
Degree is 1 × 10-3The fluorescence probe solution of M；
Step 1.2: being 1 × 10 by 1mL above-mentioned concentration-3The fluorescence probe solution of M is added in 10mL volumetric flask, then
It with solvent constant volume, shakes up, obtaining concentration is 1 × 10-4The binary channels rhodamine fluorescence probe solution of M；
Step 1.3: the concentration for taking 1mL above-mentioned is 1 × 10-4The binary channels rhodamine fluorescence probe solution of M is added to
In 10mL volumetric flask, then with solvent constant volume, shake up, obtain concentration be 1 × 10-5The binary channels rhodamine fluorescence probe of M is molten
Liquid.
It is highly preferred that the step 1.1, the solvent in 1.2,1.3 are dehydrated alcohol.
Preferably, in the step 2, the configuration method of aluminium ion stock solution includes the following steps:
Step 2.1A: 1 × 10 is accurately weighed-1The aluminum ions salt solid of mol is dissolved in deionized water, in 100mL volumetric flask
1 × 10 is configured to after interior constant volume-2The aluminium ion stock solution of M concentration；
Step 2.2A: the concentration for taking 1mL above-mentioned is 1 × 10-2The aluminium ion stock solution of M is added in the volumetric flask of 10mL,
Then with alcohol solvent constant volume, shake up, obtain concentration be 1 × 10-3The aluminium ion solution of M；
Step 2.3A: the concentration for taking 1mL above-mentioned is 1 × 10-3The aluminium ion solution of M is added in the volumetric flask of 10mL, so
Afterwards with alcohol solvent constant volume, shake up, obtain concentration be 1 × 10-4The aluminium ion solution of M；
Step 2.4A: the concentration for taking 1mL above-mentioned is 1 × 10-4The aluminium ion solution of M is added in the volumetric flask of 10mL, so
Afterwards with alcohol solvent constant volume, shake up, obtain concentration be 1 × 10-5The aluminium ion of M；
In the step 2, the configuration method of calcium ion stock solution includes the following steps:
Step 2.1B: 1 × 10 is accurately weighed-1The salt solid of mol calcium ion is dissolved in deionized water, in 100mL volumetric flask
1 × 10 is configured to after interior constant volume-2The calcium ion stock solution of M concentration；
Step 2.2B: the concentration for taking 1mL above-mentioned is 1 × 10-2The calcium ion stock solution of M is added in the volumetric flask of 10mL,
Then with alcohol solvent constant volume, shake up, obtain concentration be 1 × 10-3The ionic calcium soln of M；
Step 2.3B: the concentration for taking 1mL above-mentioned is 1 × 10-3The ionic calcium soln of M is added in the volumetric flask of 10mL, so
Afterwards with alcohol solvent constant volume, shake up, obtain concentration be 1 × 10-4The ionic calcium soln of M；
Step 2.4B: the concentration for taking 1mL above-mentioned is 1 × 10-4The ionic calcium soln of M is added in the volumetric flask of 10mL, so
Afterwards with alcohol solvent constant volume, shake up, obtain concentration be 1 × 10-5The calcium ion of M.
Preferably, in the step 3, aluminium ion solution, ionic calcium soln solvent volume ratio be the EtOH/ of 99:1
H2O；Time of repose is 1~10min.
Preferably, in the step 1, the concentration of binary channels rhodamine fluorescence probe solution is 0.8 × 10-5~1.2 ×
10-5M。
Preferably, in the step 2, the concentration of aluminium ion stock solution is 0.9~10 μM, and the concentration of calcium ion stock solution is
0.4~5.0 μM.
Preferably, in the step 3, relative intensity of fluorescence and aluminium ion, calcium ion concentration relationship are respectively as follows: y=
55.98+75.16x y=3.51+3.53z, wherein y indicates relative intensity of fluorescence；X is aluminum ions concentration, and z is calcium ion
Concentration.
Preferably, the binary channels rhodamine fluorescence probe is respectively to the detection limit of aluminium ion, calcium ion prepare liquid
0.01μM、0.28μM。
The present invention is using binary channels rhodamine fluorescence probe in EtOH/H2Network occurs with aluminium ion, calcium ion in O solution
It closes, using fluorescent emission luminosity method, excitation wavelength 556nm, 408nm, the fluorescence intensity under launch wavelength 576nm, 492nm, this
The relative intensity of fluorescence of fluorescence probe with aluminium ion, ionic calcium soln increase and increased characteristic, carry out highly sensitive
Detection.It is respectively 0.9~10 μM, in 0.4~5.0 μM of the range of linearity in the concentration of aluminium ion, calcium ion, fluorescence probe
Relative intensity of fluorescence changing value and aluminium ion, calcium ion concentration at good linear relationship, linearly dependent coefficient 0.994,
0.993, lowest detection is limited to 0.01 μM, 0.28 μM.
The present invention is using rhodamine B hydrazides and the bromo- Benzaldehyde,2-hydroxy of 4- as probe, by its fluorescence intensity with aluminium
The increase of ion and ionic calcium soln concentration and increase, fluorescence intensity degree is protected after aluminium ion and calcium ion concentration reach certain value
Hold constant characteristic, in solution aluminium ion and calcium ion carry out highly sensitive detection.The present invention utilizes the Luo Dan of fluorescence probe
The difference and schiff bases of bright spirolactams open loop and closed loop configuration to aluminum ions recognition reaction.Its mechanism is:
Al3+、Ca2+In identification process, it is complexed respectively by 1:1 than realizing coordination, but Al with N, O atom3+Rhodamine open loop is caused,
Ca2+No, complexation constant is respectively 3 × 104~5 × 104M-1、1×104~2 × 104M-1.By fluorescent spectrometry, utilize
Fluorescence intensity under 576nm, 492nm wavelength detects the content of aluminium ion and calcium ion, linearly dependent coefficient 0.994,
0.993, the range of linearity is 0.9~10 μM, 0.4~5.0 μM, and practical detection is limited to 0.01 μM, 0.28 μM.
Probe in the present invention is reacted to obtain by rhodamine B, hydrazine hydrate, the bromo- Benzaldehyde,2-hydroxy of 4-, which contains
There are N atom and O atom this two kinds of coordination atoms, adapts to the coordination property of different central ions.Its different electron donating groups
It is had differences with the medium correspondence of soda acid, thus adjustable reaction medium acid-base property, obtain actual participation atomic species sum number
Purpose is different, and then obtains a variety of coordination behaviors, and extreme enrichment Coordinative Chemistry basis, the donor that can be used as electronics provides electricity
Son to and various metals ion coordination generate metal chelate the features such as realize the distinguishing complex to heavy metal ion.
Compared with prior art, the invention has the following beneficial effects:
(1) the binary channels rhodamine fluorescence probe in the present invention has good selectivity to aluminium ion and calcium ion,
Not only facilitate in sewage treatment and bio-imaging application but also there is preferable using effect；
(2) detection of aluminium ion and calcium ion is carried out using binary channels rhodamine fluorescence probe prepared by the present invention,
Detection process is simple and convenient, high sensitivity, detection limit are low, it can be achieved that carrying out the detection of rapid sensitive to aluminium ion and calcium ion.
Detailed description of the invention
Fig. 1 (a), (b) are respectively the fluorescence intensity change in embodiment 2 after fluorescence probe addition aluminium ion, calcium ion；?
In Fig. 1 (a), (b), abscissa is wavelength of fluorescence (nm), and ordinate is fluorescence intensity；
Curve respectively represents the fluorescence intensity change song after the aluminium ion that various concentration is added, calcium ion in Fig. 2 (a), (b)
Line, aluminium ion, calcium ion concentration are followed successively by 0-6.0equiv., 0-1.0equiv. respectively；
Fig. 3 (a), (b) are respectively 4 middle probe relative intensity of fluorescence A of embodiment and the aluminium, (inspection of calcium concentration linear relationship curve
Surveying excitation wavelength is respectively 556nm, 408nm)；In Fig. 3 (a), (b), abscissa is respectively aluminium ion, calcium ion concentration, is indulged
Coordinate is fluorescence intensity；
Fig. 4 (a), (b) be respectively in embodiment 6 coexistent metallic ion it is strong to the fluorescence of the solution containing aluminium ion, calcium ion
The influence of degree.
Specific embodiment
Present invention will be further explained below with reference to specific examples.
Fluorescence probe described in following embodiment is abbreviated as RhBr, structural formula are as follows:
The specific method of rhodamine fluorescence probe detection aluminium ion and calcium ion:
Configuration 1 × 10-5The aluminium ion and calcium ion prepare liquid of M detects aluminium ion and calcium using rhodamine fluorescence probe
The method of ion, specific steps are as follows:
Step 1: rhodamine fluorescence probe being dissolved in solvent absolute ethyl alcohol, is held using solvent absolute ethyl alcohol in 100 mL
Constant volume in measuring bottle, obtaining concentration is 1.0 × 10-3The probe stock solution of M；
Step 2: aluminum nitrate and calcium chloride being dissolved in solvent absolute ethyl alcohol, using solvent absolute ethyl alcohol in 100 mL capacity
Constant volume in bottle, obtaining concentration is 1.0 × 10-3The aluminium ion and calcium ion stock solution of M；Pipetting concentration is 1.0 × 10-3The aluminium of M from
Son and calcium ion stock solution are in 100mL volumetric flask, and using solvent absolute ethyl alcohol constant volume, obtaining concentration is 1.0 × 10-3The aluminium of M
Ion and calcium ion stock solution；Pipetting concentration again is 1.0 × 10-3The aluminium ion and calcium ion stock solution of M is in 100mL volumetric flask
In, using solvent absolute ethyl alcohol constant volume, obtaining concentration is 1.0 × 10-4The aluminium ion and calcium ion stock solution of M.With same side
Aluminum nitrate and calcium chloride are dissolved in deionized water by formula, using deionized water constant volume, obtain 1.0 × 10-3The aluminium ion and calcium of M
Ion stock liquid.
Step 3: the concentration for pipetting proper volume respectively is 1.0 × 10-3M or 10-4The aluminium ion and calcium ion standard of M is molten
Probe stock solution obtained in 0.1mL step 1 is added in liquid, and 0.1mL H is added2O, using solvent absolute ethyl alcohol in 10mL volumetric flask
Middle constant volume after standing 6min, 2min, by fluorescent spectrometry, detects excitation wavelength 556nm, 408nm, launch wavelength 576nm,
Fluorescence intensity under 492nm wavelength determines that good linear relationship is presented in relative intensity of fluorescence and aluminium ion and calcium ion concentration.
Step 4: taking 0.6mL aluminium ion prepare liquid, 0.3mL calcium ion prepare liquid, concentration is 1.0 × 10-3The aluminium ion of M
Probe stock solution obtained in 0.1mL step 1 is added with calcium ion standard solution, 0.1mL H is added2O utilizes the anhydrous second of solvent
Alcohol constant volume in 10mL volumetric flask, after standing 10min, by fluorescent spectrometry, the fluorescence detected under 576nm, 492nm wavelength is strong
Degree, result 506.94,405.2.According to surveyed relative intensity of fluorescence and aluminium ion and calcium ion concentration relationship, aluminium ion is determined
With the content of aluminium ion, calcium ion in calcium ion prepare liquid, result is 6.0 μM, 3.0 μM.
Embodiment 2
Selectivity of the fluorescence probe RhBr fluorescence spectrum to metal ion:
In the CH of volume ratio 99:13CH2OH/H2In O system, metal ion Pb is being added in measurement fluorescence probe RhBr2+、Fe3 +、Cd2+、Zn2+、Mg2+、Ba2+、Mn2+、Hg2+、Cu2+、K+、Na+The fluorescence emission spectrum of front and back.
Step 1: fluorescence probe is dissolved in solvent absolute ethyl alcohol, it is default in 100mL volumetric flask using solvent absolute ethyl alcohol
Hold, obtaining concentration is 1.0 × 10-3The probe stock solution of M；
Step 2: by lead salt, molysite, cadmium salt, zinc salt, magnesium salts, chromic salts, barium salt, sodium salt, manganese salt, mercury salt, mantoquita, sylvite,
Sodium salt is dissolved in solvent deionized water, using solvent deionized water in 100mL volumetric flask constant volume, obtain concentration be 1.0 × 10- 3Each metal ion stock solution of M；
Step 3: pipetting 0.1mL concentration respectively is 1.0 × 10-230.1mL step 1 is added in each metal ion stock solution of M
Obtained in probe stock solution, be added 0.1mLH2O, using solvent absolute ethyl alcohol in 10mL volumetric flask constant volume, stand 6min,
After 2min, its fluorescence emission spectrum is detected；
It is found through experiments that, the fluorescence emission spectrum of RhBr is to Al3+、Ca2+Ion has good response.Wherein, solvent:
CH3CH2OH/H2O (99/1, v/v), concentration: 10 μM (RhBr), 10 μM (metal ion).
Embodiment 3
RhBr fluorescence emission spectrum and Al3+And Ca2+Concentration relationship:
The Al of various concentration is added3+Afterwards, measurement fluorescence probe RhBr is in CH3CH2OH/H2O (99/1, v/v) system it is glimmering
Optical emission spectroscopy figure.Wherein, solvent: CH3CH2OH/H2O (99/1, v/v), concentration: 10 μM (RhBr), Al3+Equivalent is from top to bottom
Be followed successively by 0,0.01,0.02,0.03,0.04,0.05,0.06,0.07,0.08,0.09,0.1,0.2,0.3,0.4,0.5,
0.6、0.7、0.8、0.9、1.0、2.0、3.0、4.0、 5.0、6.0。Ca2+Equivalent is followed successively by 0 from top to bottom, 0.02,0.03,
0.04、0.06、0.08、0.09、0.1、 0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.6、0.8、1.0。
Step 1: the reactive dye fluorescence probe that embodiment 1 synthesizes is dissolved in solvent absolute ethyl alcohol, it is anhydrous using solvent
Ethyl alcohol constant volume in 100mL volumetric flask, obtaining concentration is 1.0 × 10-3The probe stock solution of M；
Step 2: aluminum nitrate, calcium nitrate being dissolved in solvent absolute ethyl alcohol, using solvent absolute ethyl alcohol in 100mL capacity
Constant volume in bottle, obtaining concentration is 1.0 × 10-3The copper ion stock solution of M；Pipetting concentration is 1.0 × 10-3The copper ion deposit of M
Liquid is in 100mL volumetric flask, and using solvent absolute ethyl alcohol constant volume, obtaining concentration is 1.0 × 10-3The aluminium ion and calcium ion of M stores up
Standby liquid；Pipetting concentration again is 1.0 × 10-3The aluminium ion and calcium ion stock solution of M is anhydrous using solvent in 100mL volumetric flask
Ethyl alcohol constant volume, obtaining concentration is 1.0 × 10-4The aluminium ion and calcium ion stock solution of M；
Step 3: the concentration for pipetting proper volume respectively is 1.0 × 10-3M or 10-4The aluminium ion and calcium ion standard of M is molten
Probe stock solution obtained in 0.1mL step 1 is added in liquid, and 0.1mL H is added2O, using solvent absolute ethyl alcohol in 10mL volumetric flask
Middle constant volume after standing 6min, 2min, by fluorescent spectrometry, detects excitation wavelength 556nm, 408nm, launch wavelength 576nm,
Fluorescence intensity under 492nm wavelength.
As addition Al3+、Ca2+Concentration when reaching 0.02 μM, occur at launch wavelength 576nm, 492nm significant glimmering
Light enhancing, with being continuously increased for two metal ion species concentration, fluorescent absorption intensity is also continuously increased, 0.9~10 μM,
Preferable linear relationship is presented between 0.4~5 μM.
Embodiment 4
The measurement of standard curve and detection limit:
It is managed and is taken turns based on Stern-Volmer, measure probe (10 μM) solution in CH3CH2OH/H2The mixed solvent of O (99/1)
In to Al3+、Ca2+The range of linearity and minimum detection limit when being detected.
Step 1: fluorescence probe is dissolved in solvent absolute ethyl alcohol, it is default in 100mL volumetric flask using solvent absolute ethyl alcohol
Hold, obtaining concentration is 1.0 × 10-3The probe stock solution of M pipettes probe stock solution in 100mL volumetric flask, using solvent without
Water-ethanol constant volume in 100mL volumetric flask, obtaining concentration is 1.0 × 10-4M probe solution；
Step 2: aluminum nitrate and calcium nitrate being dissolved in solvent absolute ethyl alcohol, solvent C H is utilized3CH2OH is in 100mL capacity
Constant volume in bottle, obtaining concentration is 1.0 × 10-3The aluminium ion and calcium ion stock solution of M；Pipetting concentration is 1.0 × 10-3The aluminium of M from
Son and calcium ion stock solution are in 100mL volumetric flask, and using solvent absolute ethyl alcohol constant volume, obtaining concentration is 1.0 × 10-3The aluminium of M
Ion and calcium ion stock solution；Pipetting concentration again is 1.0 × 10-3The aluminium ion and calcium ion stock solution of M is in 100mL volumetric flask
In, using solvent absolute ethyl alcohol constant volume, obtaining concentration is 1.0 × 10-4The aluminium ion and calcium ion stock solution of M.
Step 3: the concentration for pipetting proper volume respectively is 1.0 × 10-3M or 10-4The aluminium ion and calcium ion standard of M is molten
Probe stock solution obtained in 0.1mL step 1 is added in liquid, and 0.1mL H is added2O, using solvent absolute ethyl alcohol in 10mL volumetric flask
Middle constant volume after standing 6min, 2min, by fluorescent spectrometry, detects excitation wavelength 556nm, 408nm, launch wavelength 576nm,
Fluorescence intensity under 492nm wavelength.
The concentration of aluminium ion and calcium ion increases to 6.0 × 10 from 0-5M、1.0×10-5M is surveyed after standing 6min, 2min
Examination.Probe absorbance at 576nm, 492nm is very low.With Al3+、Ca2+It is added, fluorescence intensity constantly enhances, according to Stern-
Volmer equation:
F/F0=1+KsvCq
Wherein, F0The fluorescence intensity that the probe system surveyed before and after ion is added, K are respectively indicated with FsvIt is enhancing constant,
CqFor the concentration of ion.Probe system fluorescence intensity enhances degree and good linear relationship is presented in ion concentration, such as Fig. 3 institute
Show, by calculating equation of linear regression, linearly dependent coefficient 0.994,0.993, the range of linearity is 0.9~10 μM, 0.4~5 μ
M.Practical detection is limited to 0.01 μM, 0.28 μM.Above-mentioned calculated result can be seen that probe to Al3+、Ca2+Show good inspection
Survey sensitivity, Al3+、Ca2+Identification process is simple.
Embodiment 5
Fluorescence probe RhBr detects Al3+When anti-interference:
Environment coexisting ion related to biology is probed into RhBr-Al3+CH3CH2OH/H2O (99:1) solution 576nm,
The influence of absorbance at 492nm.Wherein, solvent: CH3CH2OH/H2O (99/1, v/v), concentration: 10 μM (RhBr), 10 μM of (Al3 +), 10 μM (other ions), filled black column height is that different metal ions absorption intensity is added in RhBr, non-solid
Shade column height is in RhBr-Al3+Different metal ions absorption intensity is added in system.
Step 1: fluorescence probe is dissolved in solvent absolute ethyl alcohol, it is default in 100mL volumetric flask using solvent absolute ethyl alcohol
Hold, obtaining concentration is 1.0 × 10-3The probe stock solution of M；
Step 2: by lead salt, molysite, cadmium salt, zinc salt, magnesium salts, chromic salts, barium salt, sodium salt, manganese salt, mercury salt, sylvite, sodium salt,
Calcium salt is dissolved in solvent deionized water, using solvent deionized water in 100mL volumetric flask constant volume, obtain concentration be 1.0 × 10- 2Each metal ion stock solution of M；
Step 3: pipetting 0.1mL concentration is 1.0 × 10-3The aluminium ion stock solution of M is added obtained in 0.1mL step 1
0.1mL H is added in probe stock solution2O, using solvent absolute ethyl alcohol in 10mL volumetric flask constant volume, stand 10min after, detection
Its fluorescence emission spectrum；
Step 4: pipetting 0.1mL concentration is 1.0 × 10-3The aluminium ion stock solution of M is added obtained in 0.1mL step 1
Probe stock solution, being separately separately added into 0.1mL concentration is 1.0 × 10-3Each metal ion stock solution of M, utilizes solvent absolute ethyl alcohol
The constant volume in 10ml volumetric flask detects its fluorescence emission spectrum after standing 10min；
As can be seen from Fig. 4, other ions influence it less, and therefore, rhodamine fluorescence probe has good anti-dry
Immunity.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that under the premise of not departing from the method for the present invention, can also be made for those skilled in the art
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are equivalent embodiment of the invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical solution of the present invention
It is interior.
Claims (10)
1. a kind of binary channels rhodamine fluorescence probe for detecting aluminium ion and calcium ion, it is characterised in that: binary channels sieve
The structural formula of red bright class fluorescence probe RhBr are as follows:
2. a kind of application side of the binary channels rhodamine fluorescence probe of detection aluminium ion as described in claim 1 and calcium ion
Method, which is characterized in that step are as follows:
Step 1: preparing the binary channels rhodamine fluorescence probe solution of detection aluminium ion and calcium ion；
Step 2: preparing aluminium ion stock solution and calcium ion stock solution；
Step 3: taking binary channels rhodamine fluorescence probe solution prepared by step 1, be separately added into difference prepared by step 2
In the aluminium ion stock solution of volume, calcium ion stock solution, aluminium ion solution, the ionic calcium soln of various concentration are obtained, is stood；
Under conditions of fluorescence emission wavelengths 576nm, using aluminium ion concentration as abscissa, relative intensity of fluorescence is ordinate work
Figure, obtains RhBr-Al3+Linear relationship curve；Under conditions of fluorescence emission wavelengths 492nm, using calcium ion concentration as abscissa,
Relative intensity of fluorescence is ordinate mapping, obtains RhBr-Ca2+Linear relationship curve；
Step 4: by rhodamine fluorescence probe solution addition aluminium ion solution to be measured, ionic calcium soln, standing；In fluorescence
Under conditions of launch wavelength 576nm, the RhBr-Al according to obtained in step 33+Linear relationship curve calculates aluminium ion to be measured
Aluminum ions concentration in solution；Under conditions of fluorescence emission wavelengths 492nm, the RhBr-Ca according to obtained in step 32+Linearly
Relation curve calculates the concentration of calcium ion in ionic calcium soln to be measured.
3. the application side of the binary channels rhodamine fluorescence probe of a kind of detection aluminium ion as claimed in claim 2 and calcium ion
Method, it is characterised in that: in the step 1, the configuration method of binary channels rhodamine fluorescence probe solution includes the following steps:
Step 1.1: it is 1 that the binary channels rhodamine fluorescence probe for weighing certain molar weight is configured to 100mL concentration in a solvent
×10-3The fluorescence probe solution of M；
Step 1.2: being 1 × 10 by 1mL above-mentioned concentration-3The fluorescence probe solution of M is added in 10mL volumetric flask, then with molten
Agent constant volume shakes up, and obtaining concentration is 1 × 10-4The binary channels rhodamine fluorescence probe solution of M；
Step 1.3: the concentration for taking 1mL above-mentioned is 1 × 10-4The binary channels rhodamine fluorescence probe solution of M is added to 10mL appearance
In measuring bottle, then with solvent constant volume, shake up, obtain concentration be 1 × 10-5The binary channels rhodamine fluorescence probe solution of M.
4. the application side of the binary channels rhodamine fluorescence probe of a kind of detection aluminium ion as claimed in claim 3 and calcium ion
Method, it is characterised in that: the step 1.1, the solvent in 1.2,1.3 are dehydrated alcohol.
5. the application side of the binary channels rhodamine fluorescence probe of a kind of detection aluminium ion as claimed in claim 2 and calcium ion
Method, it is characterised in that: in the step 2, the configuration method of aluminium ion stock solution includes the following steps:
Step 2.1A: 1 × 10 is accurately weighed-1The aluminum ions salt solid of mol is dissolved in deionized water, default in 100mL volumetric flask
1 × 10 is configured to after appearance-2The aluminium ion stock solution of M concentration；
Step 2.2A: the concentration for taking 1mL above-mentioned is 1 × 10-2The aluminium ion stock solution of M is added in the volumetric flask of 10mL, then
It with alcohol solvent constant volume, shakes up, obtaining concentration is 1 × 10-3The aluminium ion solution of M；
Step 2.3A: the concentration for taking 1mL above-mentioned is 1 × 10-3The aluminium ion solution of M is added in the volumetric flask of 10mL, is then used
Alcohol solvent constant volume shakes up, and obtaining concentration is 1 × 10-4The aluminium ion solution of M；
Step 2.4A: the concentration for taking 1mL above-mentioned is 1 × 10-4The aluminium ion solution of M is added in the volumetric flask of 10mL, is then used
Alcohol solvent constant volume shakes up, and obtaining concentration is 1 × 10-5The aluminium ion of M；
In the step 2, the configuration method of calcium ion stock solution includes the following steps:
Step 2.1B: 1 × 10 is accurately weighed-1The salt solid of mol calcium ion is dissolved in deionized water, default in 100mL volumetric flask
1 × 10 is configured to after appearance-2The calcium ion stock solution of M concentration；
Step 2.2B: the concentration for taking 1mL above-mentioned is 1 × 10-2The calcium ion stock solution of M is added in the volumetric flask of 10mL, then
It with alcohol solvent constant volume, shakes up, obtaining concentration is 1 × 10-3The ionic calcium soln of M；
Step 2.3B: the concentration for taking 1mL above-mentioned is 1 × 10-3The ionic calcium soln of M is added in the volumetric flask of 10mL, is then used
Alcohol solvent constant volume shakes up, and obtaining concentration is 1 × 10-4The ionic calcium soln of M；
Step 2.4B: the concentration for taking 1mL above-mentioned is 1 × 10-4The ionic calcium soln of M is added in the volumetric flask of 10mL, is then used
Alcohol solvent constant volume shakes up, and obtaining concentration is 1 × 10-5The calcium ion of M.
6. the application side of the binary channels rhodamine fluorescence probe of a kind of detection aluminium ion as claimed in claim 2 and calcium ion
Method, it is characterised in that: in the step 3, aluminium ion solution, ionic calcium soln solvent volume ratio be the EtOH/ of 99:1
H2O；Time of repose is 1~10min.
7. the application side of the binary channels rhodamine fluorescence probe of a kind of detection aluminium ion as claimed in claim 2 and calcium ion
Method, it is characterised in that: in the step 1, the concentration of binary channels rhodamine fluorescence probe solution is 0.8 × 10-5~1.2 ×
10-5M。
8. the application side of the binary channels rhodamine fluorescence probe of a kind of detection aluminium ion as claimed in claim 2 and calcium ion
Method, it is characterised in that: in the step 2, the concentration of aluminium ion stock solution is 0.9~10 μM, and the concentration of calcium ion stock solution is
0.4~5.0 μM.
9. the application side of the binary channels rhodamine fluorescence probe of a kind of detection aluminium ion as claimed in claim 2 and calcium ion
Method, it is characterised in that: in the step 3, relative intensity of fluorescence and aluminium ion, calcium ion concentration relationship are respectively as follows: y=55.98+
75.16x, y=3.51+3.53z, wherein y indicates relative intensity of fluorescence；X is aluminum ions concentration, and z is the concentration of calcium ion.
10. the application of the binary channels rhodamine fluorescence probe of a kind of detection aluminium ion as claimed in claim 2 and calcium ion
Method, it is characterised in that: the binary channels rhodamine fluorescence probe, which limits the detection of aluminium ion, calcium ion prepare liquid, is respectively
0.01μM、0.28μM。
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| CN111896507A (en) * | 2020-06-30 | 2020-11-06 | 陕西科技大学 | Method for specifically detecting silver ions in aqueous solution by using rhodamine compounds and application thereof |
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