CN107118762B - A kind of micro Ce of detection3+Fluorescent reagent, preparation method and application - Google Patents
A kind of micro Ce of detection3+Fluorescent reagent, preparation method and application Download PDFInfo
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- CN107118762B CN107118762B CN201710515864.0A CN201710515864A CN107118762B CN 107118762 B CN107118762 B CN 107118762B CN 201710515864 A CN201710515864 A CN 201710515864A CN 107118762 B CN107118762 B CN 107118762B
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- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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- 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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- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Abstract
The present invention relates to a kind of micro Ce of detection3+Fluorescent reagent, preparation method and application, belong to fluorescence chemical sensor field.The fluorescent reagent is made of TPBD-COOH, deionized water and tetrahydrofuran；TPBD-COOH is in coherent condition in deionized water and the in the mixed solvent of tetrahydrofuran, has certain fluorescence signal, TPBD-COOH and Ce3+It is limited its Internal Rotations of Molecules further after coordination occurs, fluorescence signal can significantly increase, and reach to Ce3+The purpose of detection.Fluorescent reagent of the present invention is to Ce3+" lighting " type fluorescence response with specificity, detection sensitivity is high and response is rapid, and phosphor persistence is stablized, and has good specific selectivity；In addition, the preparation method of fluorescent reagent of the present invention is simple, and easy to operate when detection.
Description
Technical field
The present invention relates to a kind of micro Ce of detection3+Fluorescent reagent, preparation method and application, belong to fluorescence chemical sensing
Device field.
Background technique
Cerium is the highest rare earth element of content in the earth's crust, has important strategic position and unique physicochemical property, in steel
The industrial circles such as iron, non ferrous metal and their alloy, pyrophoric alloy, tail gas clean-up, permanent-magnet material, hydrogen storage material and organic catalysis,
The scientific research fields extensive applications such as agriculture degradation, Animal nutrition, biomedicine.
China's rare earth mineral reserve very abundant, accounts for the 80% of world's known reserve, and the content of cerium then accounts for rare earth element total amount
50%.Since production technological break-through and the market expansion, China has become the big producer of cerium and its rare-earth mixed metal, answers
With big country and big export country, also to environmental protection, more stringent requirements are proposed for Rare-earth Industry booming.Therefore, raw to industry
It produces and is had a very important significance with the micro discarded metal cerium progress specific quantification detection generated in scientific research.
Mainly there are inductively coupled plasma atomic emission spectrometry, x-ray fluorescence light for the detection method of cerium at present
Spectrometry, atomic absorption spectrography (AAS), potentiometric titration and photometry etc..Since there are expensive equipments, testing cost for preceding several method
The defects of high, poor to other metals interference resistance, photometry becomes the main means (Yang Xiang for carrying out trace detection to cerium at present
The progress hydrometallurgy of precious photometry measurement cerium, 2009,28,1,56-63).Cerium is in the earth's crust generally with Ce4+Ion
And Ce3+The form of ion exists, due to Ce4+The hydrolysis ability of ion is stronger, and the Ce elements in soil are generally with Ce4+Ion
Form is enriched with.In the detection of photometry, conventional spectrophotometry and Catalytic-Kinetic Spectrophotometric are based primarily upon color developing agent and cerium
Ion (Ce4+And Ce3+) complex compound is formed, or utilize Ce4+The oxidation decoloration property of ion is measured, due to Ce3+From
Son is based on Ce there are less3+The measurement of ion is rarely reported.There are developing sensitivity is not high enough and metal ion disturbance for photometry
The problem of；And the means of testing such as Ultraviolet Photometric Method and stoichiometry photometry then carry out pretreatment and spectroscopic data calculates,
Increase the workload of test；Fluorescent reagent method can realize linearity test, but this in lower detection limit and detection range
The research of aspect is seldom, and portion of reagent is fluorescent quenching type (Susner, M.A.；Conner,B.S.Flux growth and
characterization of Ce-substituted Nd2Fe14B single crystals.Journal of
Magnetism and Magnetic Materials, 2017,434,1-9), realize that accurate quantitative analysis detection acquires a certain degree of difficulty.
2001, Tang Benzhong seminar reported " aggregation-induced emission (AIE) " phenomenon (Luo, J D.；Xie,Z.L.；
Lam,J.W.Y.Aggregation-induced emission of 1-methyl-1,2,3,4,5-
Pentaphenylsilole. Chem.Commun., 2001,18,1740-1741), due to its unique " lighting " effect, AIE
Molecule is widely used in chemistry and bio-sensing, such as Al3+、Hg2+, protein etc., have not seen AIE points of " lighting " type at present
Son is applied to Ce3+Detection.
Summary of the invention
Existing chemical reagent is mostly based on Ce to the detection of cerium4+The oxidisability and colour rendering of ion, that there are sensitivity is lower,
Other metal ions have the problems such as interference, and one of the objects of the present invention is to provide a kind of micro Ce of detection3+Fluorescent reagent, institute
Fluorescent reagent is stated to Ce3+" lighting " type fluorescence response with specificity, detection sensitivity is high and response is rapid, and phosphor persistence is steady
It is fixed, and there is good specific selectivity；The second purpose is to provide a kind of micro Ce of detection3+Fluorescent reagent preparation method,
The preparation method is simple, easy to operate.
The purpose of the present invention is realized by the following technical scheme:
A kind of micro Ce of detection3+Fluorescent reagent, the fluorescent reagent is made of TPBD-COOH and mixed solvent I；
Wherein, the TPBD-COOH is (1Z, 3Z)-Isosorbide-5-Nitrae-two (4- carboxyl) phenyl-Isosorbide-5-Nitrae-two (3- thiophene) base -1,3-
The abbreviation of butadiene, structural formula are as follows:
The mixed solvent I is mixed with tetrahydrofuran according to the volume ratio of 8.5:1.5~9.5:0.5 by deionized water
It arrives；
Concentration of the TPBD-COOH in mixed solvent I is 1 × 10-3Mol/L~1 × 10-5mol/L。
The TPBD-COOH is prepared with the following method, the specific steps are as follows:
(1) by the bromo- 1,3- butadiene of (1Z, 3Z) -1,4- two (4- methoxycarbonyl group) phenyl -1,4- two, 3 thienylboronic acid, four
(triphenylphosphine) palladium and carbonate are dissolved in mixed solvent II, under the conditions of anhydrous and oxygen-free, are stirred to react in 70 DEG C~80 DEG C
10h~14h, separating-purifying obtain (1Z, 3Z)-Isosorbide-5-Nitrae-two (4- methoxycarbonyl group) phenyl-Isosorbide-5-Nitrae-two (3- thiophene) base -1,3- fourth
Diene, abbreviation TPBD；
(2) TPBD is dissolved in mixed solvent III, adds excessive sodium hydrate, at 65 DEG C~75 DEG C react 8h~
After 12h, the organic phase in reaction system is removed, the pH for adding hydrochloric acid to reaction system is 1~2, and separating-purifying obtains
TPBD-COOH；
Wherein, the bromo- 1,3-butadiene of (1Z, 3Z)-Isosorbide-5-Nitrae-two (4- methoxycarbonyl group) phenyl-Isosorbide-5-Nitrae-two, 3 thienylboronic acid, four
The molar ratio of (triphenylphosphine) between palladium and carbonate is 1:(8~10): (0.03~0.05): (15~30)；The mixing is molten
Agent II is by toluene and tetrahydrofuran according to (1.5~4): 1 volume ratio is mixed to get；The mixed solvent III is by equal bodies
The tetrahydrofuran and water of product ratio form.
The preferred potassium carbonate of carbonate.
In step (1), it is preferred to use column chromatography carries out separating-purifying, and column chromatographs used eluant, eluent by methylene chloride
It is formed with petroleum ether, and the preferred 2:1 of the volume ratio of methylene chloride and petroleum ether.
The soda acid being added in step (2) is excess, to ensure that TPBD reacts completely, mole of sodium hydroxide and TPBD
Ratio is preferably not less than 10, and pH is adjusted to 1~2 by the hydrochloric acid content of addition.
The Ce that fluorescent reagent concentration suitable for solution to be measured is 0.318 μ of μ g/mL~2.765 g/mL3+Determined
Amount detection；If containing Ce in solution to be measured4+When, alcohol is first added into solution to be measured makes Ce4+It is reduced into Ce3+, then to solution to be measured
In Ce3+Quantitative detection is carried out, realizes Ce in solution to be measured indirectly4+And Ce3+Common presence or Ce4+Determine when individualism
The backbone c atoms number of amount detection, the alcohol is not more than 4, and has primary hydroxyl and secondary hydroxyl simultaneously.
A kind of micro Ce of detection of the present invention3+Fluorescent reagent preparation method, the method comprises the following steps:
TPBD-COOH is dissolved in mixed solvent I, is uniformly mixed, obtains the fluorescent reagent.
The utility model has the advantages that
(1) fluorescent reagent of the present invention is to Ce3+There is the fluorescence response of specificity, TPBD-COOH is in mixed solvent I
In coherent condition, there is certain fluorescence signal；Ce is added3+Afterwards, TPBD-COOH and Ce3+Coordination occurs, makes its molecule
It is limited to be inside rotated into a step, the fluorescence signal of fluorescent reagent significantly increases.
(2) fluorescent reagent of the present invention is to Ce3+Sensitivity with higher is detected, the minimum detectability of this method is used
For 0.318 μ g/mL；And within the scope of 0.318 μ of μ g/mL~2.765 g/mL, Ce3+Concentration and fluorescence signal intensity in good
Linear correlation, can be realized in the range to Ce3+Quantitative detection；In addition, the fluorescent reagent is to Ce3+Detection it is non-
Almost Ce is being added in Chang Kuaijie, the fluorescence intensity of fluorescent reagent3+While just significantly increase, and fluorescence intensity enhancing after at any time
Between extend and no longer have significant change, " lighting " effect with real-time stabilization.
(3) fluorescent reagent of the present invention is to Ce3+The detection of ion has high selectivity, specificity, for other kinds
The metal ion of class, such as: Ag+、Al3+、Ba2+、Ca2+、Cd2+、Hg2+、Mg2+、Pb2+、 Cr3+、Zn2+、K+、Na+It is rung Deng equal without obvious
It answers.
(4) fluorescent reagent of the present invention is to Ce4+There is weaker response, Ce can be fast implemented by the way that alcohols is added3+
And Ce4+Differentiation.
(5) preparation method of fluorescent reagent of the present invention is simple；And when detecting, solution to be measured is not needed to carry out
Pretreatment, even if the metal ion of other frequent species (removes Hg2+、Fe2+、Fe3+Exist outside) and nor affects on fluorescent reagent to Ce3+
Detection effect.
Detailed description of the invention
Fig. 1 is that the fluorescence intensity change rate containing different metal ions solution is added into fluorescent reagent described in embodiment 3
Comparison diagram；It wherein, is successively from left to right a:Ag+, b:Al3+, c:Ba2+, d:Ca2+, e:Cd2+, f:Ce3+, g:Cr3+, h:Fe3+,
i:Hg2+, j:K+, k:Mg2+, l:Na+, m:Pb2+, n:Zn2+, o:Ce3++ Cr3++Al3+, p:Ce3++Ca2++Zn2+, q:Ce3++K++
Na+, r:Ce3++Fe2+, s:Fe2+, t:Ce3+ +Fe3+, u:Ce4+, v:Ce4++ 1,2-PD, I/I0Indicate TPBD-COOH fluorescence
The fluorescence intensity change rate of reagent.
Fig. 2 is that different concentration of Ce is added into fluorescent reagent described in embodiment 43+Fluorogram.
Fig. 3 is the fluorescence intensity change rate of fluorescent reagent described in embodiment 4 with Ce3+The curve of concentration variation and its fitting are straight
Line chart
Fig. 4 is that different concentration of Ce is added into fluorescent reagent described in embodiment 53+Later, fluorescence intensity changes over time
Fluorogram.
Fig. 5 is the Ce that different mol ratio is added into fluorescent reagent described in embodiment 63+And Ce4+Mixed solution, and be added
The comparison diagram of fluorescence intensity change rate before and after 1,2- propylene glycol.
Specific embodiment
The present invention is described in detail in the following with reference to the drawings and specific embodiments, but not limited to this.
The main agents information mentioned in following embodiment is shown in Table 1；Key instrument and facility information are shown in Table 2.
Table 1
Table 2
The excitation wavelength of sepectrophotofluorometer described in following embodiment is 380nm.
Embodiment 1
A kind of micro Ce of detection3+Fluorescent reagent preparation method, the method comprises the following steps:
(1) preparation of TPBD
Take the bromo- 1,3- butadiene 200mg of (1Z, 3Z) -1,4- two (4- methoxycarbonyl group) phenyl -1,4- two, 3 thienylboronic acid
460mg, tetrakis triphenylphosphine palladium 20.9mg and potassium carbonate 1.2g are added into the twoport flask of 250mL, vacuumize, nitrogen charging
Gas three times, injects II (V of 120mL mixed solvent laterToluene:VTetrahydrofuran=3:1)；Under the conditions of nitrogen protection, it is heated to 77 DEG C instead
Answer 12h, using methylene chloride and petroleum ether volume ratio for 2:1 mixed solution as eluant, eluent, obtained using column chromatography purification & isolation
To faint yellow solid powder；
Pass through the faint yellow solid known to nuclear magnetic resonance chemical analyser, Fourier Transform Infrared Spectrometer and mass-spectroscopic characterization
Powder is TPBD, and nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, infrared and mass spectrometric data are as follows:
1H-NMR(400MHz,CDCl2)δ(ppm):3.91(m,6H),7.01(s,2H),7.07(d,2H), 7.18-7.50
(m,8H),7.95-7.97(d,4H)；
13C-NMR(400MHz,CDCl3)δ(ppm):166.35,139.20,129.35,128.04,127.83,
125.75,52.10；
FTIR:1700cm-1For carbonyl characteristic peak, 1340cm-1For methyl characteristic peak, 1400cm-1~1600cm-1For phenyl ring
With thiphene ring characteristic peak, 900cm-1~500cm-1For phenyl ring and thiphene ring C-H out-of-plane bending vibration peak；
MS(MALDI-TOF):calcd.For C28H22O4S2,486.1；found,486.
(2) preparation of TPBD-COOH
The TPBD of 150mg is dissolved in III (V of 50mL mixed solventTetrahydrofuran:VWater=1:1) in, addition 2g sodium hydroxide, 70 DEG C
After back flow reaction 12h, revolving removes tetrahydrofuran, and it is 1~2 that hydrochloric acid, which is added, to pH, and filtering receives filter cake, obtains yellow solid；
It is by the yellow solid known to nuclear magnetic resonance chemical analyser, Fourier Transform Infrared Spectrometer and mass-spectroscopic characterization
TPBD-COOH, nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, infrared and mass spectrometric data are as follows:
1H-NMR(400MHz,C2D6SO)δ(ppm):6.89(s,2H),7.01(d,2H),7.38(d,4H),7.63 (s,
2H),7.72(m,2H),7.89(m,4H),12,91(s,2H)；
13C-NMR(400MHz,C2D6SO) δ (ppm): 167.19,146.26,138.96,130.23,127.34；
FTIR:3400cm-1For carboxyl characteristic peak, 1700cm-1For carbonyl characteristic peak, 1400cm-1~1600cm-1For phenyl ring
With thiphene ring characteristic peak, 900cm-1~500cm-1For phenyl ring and thiphene ring C-H out-of-plane bending vibration peak；
MS(MALDI-TOF):calcd.for C26H18O4S2,458.06；found,458.054.
(3) preparation of the fluorescent reagent
1.145mg TPBD-COOH is dissolved in 25mL tetrahydrofuran, being configured to concentration is 1 × 10-4The mother liquor of mol/L
Ⅰ；It takes 300 μ L mother liquors I to be added in sample bottle, then 2700 μ L deionized waters is added into sample bottle, shaken well obtains described
Fluorescent reagent.
Embodiment 2
A kind of micro Ce of detection3+Fluorescent reagent preparation method, the method comprises the following steps:
(1) preparation of TPBD
Take the bromo- 1,3- butadiene 500mg of (1Z, 3Z) -1,4- two (4- methoxycarbonyl group) phenyl -1,4- two, 3 thienylboronic acid
1.3g, tetrakis triphenylphosphine palladium 60mg and potassium carbonate 4g are added into the twoport flask of 500mL, vacuumize, inflated with nitrogen three
It is secondary, II (V of 250mL mixed solvent is injected laterToluene:VTetrahydrofuran=3:2)；Under the conditions of nitrogen protection, it is heated to 77 DEG C of reactions
12h, using methylene chloride and petroleum ether volume ratio for 2:1 mixed solution as eluant, eluent, obtained using column chromatography purification & isolation
Faint yellow solid powder；
Pass through the faint yellow solid known to nuclear magnetic resonance chemical analyser, Fourier Transform Infrared Spectrometer and mass-spectroscopic characterization
Powder is TPBD, and nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, infrared and mass spectrometric data are as follows:
1H-NMR(400MHz,CDCl2)δ(ppm):3.91(m,6H),7.01(s,2H),7.07(d,2H), 7.18-7.50
(m,8H),7.95-7.97(d,4H)；
13C-NMR(400MHz,CDCl3)δ(ppm):166.35,139.20,129.35,128.04,127.83,
125.75,52.10；
FTIR:1700cm-1For carbonyl characteristic peak, 1340cm-1For methyl characteristic peak, 1400cm-1~1600cm-1For phenyl ring
With thiphene ring characteristic peak, 900cm-1~500cm-1For phenyl ring and thiphene ring C-H out-of-plane bending vibration peak；
MS(MALDI-TOF):calcd.For C28H22O4S2,486.1；found,486.
(2) preparation of TPBD-COOH
The TPBD of 250mg is dissolved in III (V of 150mL mixed solventTetrahydrofuran:VWater=1:1) in, 5 g sodium hydroxides of addition, 70
After DEG C back flow reaction 12h, revolving removes tetrahydrofuran, and it is 1~2 that hydrochloric acid, which is added, to pH, and filtering receives filter cake, obtains yellow solid；
It is by the yellow solid known to nuclear magnetic resonance chemical analyser, Fourier Transform Infrared Spectrometer and mass-spectroscopic characterization
TPBD-COOH, nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, infrared and mass spectrometric data are as follows:
1H-NMR(400MHz,C2D6SO)δ(ppm):6.89(s,2H),7.01(d,2H),7.38(d,4H),7.63 (s,
2H),7.72(m,2H),7.89(m,4H),12,91(s,2H)；
13C-NMR(400MHz,C2D6SO) δ (ppm): 167.19,146.26,138.96,130.23,127.34；
FTIR:3400cm-1For carboxyl characteristic peak, 1700cm-1For carbonyl characteristic peak, 1400cm-1~1600cm-1For phenyl ring
With thiphene ring characteristic peak, 900cm-1~500cm-1For phenyl ring and thiphene ring C-H out-of-plane bending vibration peak.
MS(MALDI-TOF):calcd.for C26H18O4S2,458.06；found,458.054.
(3) preparation of the fluorescent reagent
1.145mg TPBD-COOH is dissolved in 25mL tetrahydrofuran, being configured to concentration is 1 × 10-4The mother liquor of mol/L
Ⅰ；It takes 300 μ L mother liquors I to be added in sample bottle, then 2700 μ L deionized waters is added into sample bottle, shaken well obtains described
Fluorescent reagent.
Embodiment 3
Prepared fluorescent reagent is to Ce in embodiment 13+Specific recognition test:
Fluorescent reagent prepared by 22 parts of embodiments 1 is taken, and is marked according to the lexicographic order of a~v, and every part of fluorescent reagent
Volume be 3mL；The aqueous solution containing different metal ions is added into 22 parts of fluorescent reagents, it is 10 that 50 μ L concentration are added in a- 4The Ag of mol/L+, it is 10 that 50 μ L concentration are added in b-4The Al of mol/L3+, it is 10 that 50 μ L concentration are added in c-4The Ba of mol/L2+, d
50 μ L concentration of middle addition are 10-4The Ca of mol/L2+, it is 10 that 50 μ L concentration are added in e-4The Cd of mol/L2+, it is dense that 50 μ L are added in f
Degree is 10-4The Ce of mol/L3+, it is 10 that 50 μ L concentration are added in g-4The Cr of mol/L3+, it is 10 that 50 μ L concentration are added in h-4mol/L
Fe3+, it is 10 that 50 μ L concentration are added in i-4The Hg of mol/L2+, it is 10 that 50 μ L concentration are added in j-4The K of mol/L+, it is added in k
50 μ L concentration are 10-4The Mg of mol/L2+, it is 10 that 50 μ L concentration are added in l-4The Na of mol/L+, it is 10 that 50 μ L concentration are added in m- 4The Pb of mol/L2+, it is 10 that 50 μ L concentration are added in n-4The Zn of mol/L2+, it is 10 that 50 μ L concentration are added in o-4The Ce of mol/L3+、
50 μ L concentration are 10-4The Cr of mol/L3+And 50 μ L concentration be 10-4The Al of mol/L3+, it is 10 that 50 μ L concentration are added in p-4mol/
The Ce of L3+, 50 μ L concentration be 10-4The Ca of mol/L2+And 50 μ L concentration be 10-4The Zn of mol/L2+, 50 μ L concentration are added in q
It is 10-4The Ce of mol/L3+, 50 μ L concentration be 10-4The K of mol/L+And 50 μ L concentration be 10-4The Na of mol/L+, 50 μ are added in r
L concentration is 10-4The Ce of mol/L3+It is 10 with 50 μ L concentration-4The Fe of mol/L2+, it is 10 that 50 μ L concentration are added in s-4The Fe of mol/L2 +, it is 10 that 50 μ L concentration are added in t-4The Ce of mol/L3+It is 10 with 50 μ L concentration-4The Fe of mol/L3+, 50 μ L concentration, which are added, in u is
10-4The Ce of mol/L4+, it is 10 that 50 μ L concentration are added in v-4The Ce of mol/L4+With 50 μ L 1,2- propylene glycol.With fluorescence spectrophotometer light
Degree meter measures the initial fluorescent intensity I of the fluorescent reagent respectively0And 22 parts of fluorescence after different metal ions aqueous solution are added
The fluorescence intensity I of reagent, and according to the fluorogram of measurement result drafting fluorescent reagent, as shown in Figure 1.
By the test result of h, i, s in Fig. 1 it is found that the fluorescent reagent is to Hg2+、Fe2+、Fe3+Type response is quenched；Though
Contain Ce in right t3+, but the metal cations Fe of type is quenched3+Prior to Ce3+Coordination is carried out with TPBD-COOH, so t
In do not light response, that is to say, that there are it is above-mentioned type ion is quenched when, first can remove interfering ion in advance with other reagents,
Ce is carried out again3+Detection.According to the test result of u, v it is found that the fluorescent reagent is to Ce4+There are weaker response, i.e. fluorescence
Intensity has slight enhancing, and after 1,2-PD is added as reducing agent, fluorescence intensity significantly rises (intensification factor is about 3.8),
With addition equivalent Ce3+When quite (intensification factor is about 4.0), this is because 1,2-PD be oxidized after product influence,
To make its fluorescence intensity that equivalent Ce slightly below be added3+Ion.According to the test result of Fig. 1 it is found that the fluorescent reagent is to Ce3 +Response is lighted with specificity, other metal ions (Ag+、Al3+、Ba2+、 Ca2+、Cd2+、Hg2+、Mg2+、Pb2+、Cr3+、Zn2+、K+、Na+) without obviously variation is lighted, i.e., the described fluorescent reagent may be implemented to Ce3+Specificity detection effect.
Embodiment 4
Using fluorescent reagent of the present invention to Ce3Concentration carries out the acquisition of the standard curve of quantitative detection:
It takes fluorescent reagent prepared by 3mL embodiment 1, then by 100 μ L concentration is 1 × 10-4The Ce of mol/L3+Ionized water
20 additions of solution point, are added Ce every time3+The amount of deionized water solution is 5 μ L.The examination of the fluorescence described in fluorescence spectrophotometer measurement
The initial fluorescent intensity I of agent0And Ce is added every time3+Fluorescence intensity I after deionized water solutioni, and it is glimmering according to measurement result drafting
The fluorogram of light reagent, as shown in Figure 2.
As can be seen from FIG. 2, with Ce3+The luminous intensity of the increase of concentration, the fluorescent reagent gradually increases, to Ce3+From
After sub- aqueous solution additional amount reaches 70 μ L, fluorescence intensity tends towards stability.It takes within the scope of 0~70 μ L, each Ce3+The corresponding fluorescence of concentration
The highest point of intensity, with Ce3+The corresponding mapping of concentration, obtains Fig. 3, Fig. 3 is quantitative detection Ce3+Canonical plotting.
From the figure 3, it may be seen that the fluorescent reagent is to Ce3+Lowest detection be limited to 0.318 μ g/mL；The change of the fluorescent reagent
Rate (Ii-I0)/I0With Ce3+Linear relationship, linear equation table is presented within the scope of 0.318 μ of μ g/mL~2.765 g/mL in concentration
It is shown as: Y=-0.2239+0.28092X, R2=0.99519, wherein Y indicates (Ii-I0)/I0, X expression Ce3+Ion concentration, R table
The linear degree of correlation.
Embodiment 5
Fluorescent reagent of the present invention is to Ce3+Sensitivity technique test:
Fluorescent reagent prepared by 3mL embodiment 1 is taken, then it is 1 × 10 that concentration is added into fluorescent reagent in batches- 4The Ce of mol/L3+Deionized water solution, and Ce is added every time3+The amount of deionized water solution is 5 μ L.With fluorescence spectrophotometer measurement institute
State the initial fluorescent intensity I of fluorescent reagent0And Ce is added every time3+Fluorescence intensity I after deionized water solutioni, and be added to each
Ce3+The retest of fluorescent reagent after deionized water solution a length of 120s (primary every 30s detection) when carrying out, obtains Fig. 4.
As shown in Figure 4, the fluorescent reagent is to Ce3+" lighting " type respond sensitivity with higher and stability,
Ce3+Ion is added in 10s, and fluorescence intensity enhances, and significant change then no longer occurs.
Embodiment 6
Fluorescent reagent of the present invention is to Ce3+And Ce4+Half-quantitative detection test:
It is 1 × 10 by 30 μ L concentration-4The Ce of mol/L3+Deionized water solution and 60 μ L concentration are 1 × 10-4The Ce of mol/L4+
Deionized water solution mixing, obtains test specimens A；Test specimens A is added in fluorescent reagent prepared by 3mL embodiment 1, fluorescence is used
The initial fluorescent intensity I of fluorescent reagent described in spectrophotometer measurement0And the fluorescence intensity I after test specimens A is addedA1；Again to
Excessive 1,2- propylene glycol is added in fluorescent reagent containing test specimens A, 1,2-PD is as reducing agent and Ce4+Ion carries out
Reaction, the fluorescence intensity I after being reacted with fluorescence spectrophotometer measurementA2, as a result it is detailed in Fig. 5.
It is 1 × 10 by 45 μ L concentration-4The Ce of mol/L3+Deionized water solution and 45 μ L concentration are 1 × 10-4The Ce of mol/L4+
Deionized water solution mixing, obtains test specimens B；It is 1 × 10 by 60 μ L concentration-4The Ce of mol/L3+Deionized water solution and 30 μ L concentration
It is 1 × 10-4The Ce of mol/L4+Deionized water solution mixing, obtains test specimens C；90 μ L concentration are 1 × 10-4The Ce of mol/L3+Ion
Aqueous solution is denoted as comparative sample D.
Test specimens A is replaced with into test specimens B, test specimens C, comparative sample D respectively, other test conditions are constant, repeat above-mentioned
Operation measures test specimens B, test specimens B+1,2- propylene glycol, test specimens C, test specimens C+1,2- propylene glycol, comparative sample is added respectively
Fluorescence intensity I after DB1、IB2、IC1、IC2、ID, test result is detailed in Fig. 5.
According to IA1、IB1、IC1Test result it is found that Ce in initial testing sample3+Content is more, and fluorescence intensity is stronger,
Fluorescence intensity and Ce3+And Ce4+Molar ratio have sxemiquantitative relationship；According to IA2、IB2、 IC2Test result it is found that be added
After 1,2-PD, compared to IA1、IB1、IC1, corresponding fluorescence intensity is remarkably reinforced, intensification factor and individually plus
Enter isometric Ce3+The fluorescence intensity I of deionized water solutionDQuite, identical as the experimental result of u, v in embodiment 3.Therefore, right
Than the fluorescence intensity before and after 1,2- propylene glycol is added in solution to be measured, can determine in solution to be measured whether contain Ce4+；Moreover,
For containing Ce4+Solution to be measured, 1,2-PD can first be added and carry out redox reaction, then to the Ce after reduction3+
Quantitative detecting analysis is carried out, to realize Ce in test solution to be measured3+And Ce4+Or Ce4+The quantitative detecting analysis of content.
The present invention includes but is not limited to above embodiments, it is all carried out under the principle of spirit of that invention it is any equivalent
Replacement or local improvement, all will be regarded as within protection scope of the present invention.
Claims (7)
1. a kind of micro Ce of detection3+Fluorescent reagent, it is characterised in that: the fluorescent reagent is by TPBD-COOH and mixed solvent I
Composition；
Wherein, the structural formula of the TPBD-COOH is as follows:
The mixed solvent I is to be mixed to get by deionized water and tetrahydrofuran according to the volume ratio of 8.5:1.5~9.5:0.5
's；
Concentration of the TPBD-COOH in mixed solvent I is 1 × 10-5Mol/L~1 × 10-3mol/L。
2. a kind of micro Ce of detection according to claim 13+Fluorescent reagent, it is characterised in that: the TPBD-COOH is
It is prepared with the following method, the specific steps are as follows:
(1) by the bromo- 1,3- butadiene of (1Z, 3Z) -1,4- two (4- methoxycarbonyl group) phenyl -1,4- two, 3 thienylboronic acid, four (three
Phenylphosphine) palladium and carbonate is dissolved in mixed solvent II, under the conditions of anhydrous and oxygen-free, 10h is stirred to react in 70 DEG C~80 DEG C
~14h, separating-purifying obtain TPBD；
(2) TPBD is dissolved in mixed solvent III, adds excessive sodium hydrate, 8h~12h is reacted at 65 DEG C~75 DEG C
Afterwards, the organic phase in reaction system is removed, the pH for adding hydrochloric acid to reaction system is 1~2, and separating-purifying obtains TPBD-
COOH；
Wherein, the bromo- 1,3-butadiene of (1Z, 3Z)-Isosorbide-5-Nitrae-two (4- methoxycarbonyl group) phenyl-Isosorbide-5-Nitrae-two, 3 thienylboronic acid, four (three
Phenylphosphine) molar ratio between palladium and carbonate is 1:(8~10): (0.03~0.05): (15~30)；The mixed solvent II
Be by toluene and tetrahydrofuran according to (1.5~4): 1 volume ratio is mixed to get；The mixed solvent III is by comparing in equal volume
Tetrahydrofuran and water form.
3. a kind of micro Ce of detection according to claim 23+Fluorescent reagent, it is characterised in that: in step (1), use
Column chromatography carries out separating-purifying, and column chromatographs used eluant, eluent and is made of the methylene chloride that volume ratio is 2:1 with petroleum ether.
4. a kind of micro Ce of detection according to claim 23+Fluorescent reagent, it is characterised in that: in step (2), hydrogen-oxygen
The molar ratio for changing sodium and TPBD is not less than 10.
5. one kind detects micro Ce as described in claim 13+Fluorescent reagent preparation method, it is characterised in that: the side
Steps are as follows for method:
TPBD-COOH is dissolved in mixed solvent I, is uniformly mixed, obtains the fluorescent reagent.
6. one kind detects micro Ce as described in claim 13+Fluorescent reagent application, it is characterised in that: fluorescence examination
The Ce that it is 0.318 μ of μ g/mL~2.765 g/mL to concentration in solution to be measured that agent, which is used for,3+Carry out quantitative detection.
7. a kind of micro Ce of detection according to claim 63+Fluorescent reagent application, it is characterised in that: solution to be measured
In contain Ce4+When, alcohol is first added into solution to be measured makes Ce4+It is reduced into Ce3+, then to the Ce in solution to be measured3+It is detected,
It realizes indirectly to Ce in solution to be measured4+And Ce3+Or Ce4+Quantitative detection；
Wherein, the backbone c atoms number of the alcohol is not more than 4, and has primary hydroxyl and secondary hydroxyl simultaneously.
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