CN108279224B - A method of persulfuric acid ion concentration is detected with conjugated polyelectrolytes-silver - Google Patents

A method of persulfuric acid ion concentration is detected with conjugated polyelectrolytes-silver Download PDF

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CN108279224B
CN108279224B CN201810085024.XA CN201810085024A CN108279224B CN 108279224 B CN108279224 B CN 108279224B CN 201810085024 A CN201810085024 A CN 201810085024A CN 108279224 B CN108279224 B CN 108279224B
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conjugated polyelectrolytes
silver
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nano silver
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黄红梅
肖毅
史慧珍
杜慧凤
何晓晓
张友玉
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Hunan Normal University
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Abstract

A method of persulfuric acid ion concentration is detected with conjugated polyelectrolytes-silver, comprising the following steps: (1) it is conjugated polyelectrolytes aqueous solution, Nano silver solution and buffer is soluble in water, after being stirred to react, uniform system is obtained, measures its fluorescence intensity F0；(2) in the uniform system obtained by step (1), the solution for containing over cure acid ion to be measured is added, after being stirred to react, measures its fluorescence intensity F；(3) Y=(F is calculated0- F)/F0, then by formula Y=0.526 × log of relationship between expression over cure acid ion and fluorescence intensityC(S2O8 2‑)+3.044, R=0.955, obtain persulfuric acid ion concentration.Simple and easy, accurate, rapid, the selective good, high sensitivity of detection method, lowest detection are limited to 9 × 10‑7 Mol/L, and 1 × 10‑6~9 × 10‑5It is detected in the range of mol/L linear good.

Description

A method of persulfuric acid ion concentration is detected with conjugated polyelectrolytes-silver
Technical field
The present invention relates to a kind of methods for detecting persulfuric acid ion concentration, and in particular to a kind of to use conjugated polyelectrolytes- The method of silver detection persulfuric acid ion concentration.
Background technique
Persulfate has strong oxidizing property, has been widely used for the decontamination of water and soil, circuit board fabrication, cosmetics and poly- Many aspects such as conjunction.For example, the ammonium persulfate as excellent initiator can be used for aqueous adhesive synthesis.Aqueous binder is normal For bonding a kind of important raw material of cigarette and filter tip.As the important component of cigarette, the ingredient of aqueous binder It is one of the key influence factor of cigarette quality and class.Therefore, the method for harmful chemical in aqueous binder has been detected By pay attention to day by day.Often there is some chemical substances such as ammonium persulfate that may endanger respiratory system and siberian crabapple in aqueous binder System, leads to or aggravates such as asthma and dermoreaction disease.Therefore, content of the monitoring ammonium persulfate in aqueous binder has very much The method of necessity, detection over cure acid group also has gradually developed.
2000, F. De Oliveira etc. detected over cure by voltammetry with the platinum disk electrode that Prussian blue (PB) is modified The content of acid group, 5 × 10-5~3 × 10-3Have within the scope of M it is preferable linear (Microchem. J., 2000, 64, 155-159)；2003, F. De Oliveira etc. was infused using the glass carbon disk electrode of Prussian Blue Film Modified through flowing again The content of Amperometric Determination persulfate is penetrated, detection is limited to 9.0 × 10-5M(Sensors, 2003,3,371-380)； 2015, Zhao etc. reacted persulfate rapidly with methylene blue by microwave activation, realized methylene blue quick decolorization, from And reaching quick, the easy detection to persulfate, this method has good linear, minimum inspection within the scope of 0~1.5 mM It surveys limit and reaches 2.8 × 10-6M(J. Environ. Sci., 2015,31,235-239)；2016, Xu etc. was utilized low dense The persulfate of degree can make absorption of the triangular silver nanosheet at 670 nm have apparent decrease, to realize S2O8 2-Than Color detection, this method have good linear relationship in 0.1~0.7 mM, and detection is limited to 1 × 10-5M(Anal. Methods, 2016,8,1483-1488).But above technical process is cumbersome, the high requirements on the equipment, analytic process is time-consuming and laborious, Sensitivity for analysis is not high, is unfavorable for the actual production and monitoring application of the usually persulfate containing low concentration.
Fluorescence detection have the characteristics that it is simple, quick, sensitive, without marking, be widely used in sulfurous acid hydrogen radical ion or Sulfite ion (CN106496197A), sulphion (CN103323440A, CN102004100A, CN106442448A), sulphur The detection of thiosulfuric acid radical ion (CN106770103A) etc., but the synthesis of its probe is complicated, and probe is often to cell or organism With certain toxicity, detection process is complicated, time-consuming, and synthetic method is not easy to grasp.Conjugated polymer is a kind of novel highly sensitive Fluorescence sense detection platform, have patent report for fluorine ion (CN105295009A), copper ion (CN101824139A), The detection of biomolecule and cell (CN105348493A) etc. such as ATP(CN105348493A) and BSA(CN103588960A), but It is that most conjugated polymer probe can only be dissolved in organic solvent, and water-soluble poor, synthesis process is cumbersome time-consuming.
Summary of the invention
The present invention provides one further the technical problem to be solved is that, overcome drawbacks described above of the existing technology Kind is simple and easy, accurate, rapid, highly sensitive, and lowest detection is limited to 9 × 10-7 Mol/L, and detect linear good poly- with conjugation Electrolyte-silver detection persulfuric acid ion concentration method.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of to be detected with conjugated polyelectrolytes-silver The method of sulfate ion concentration, comprising the following steps:
(1) conjugated polyelectrolytes aqueous solution, Nano silver solution and buffer is soluble in water, after being stirred to react, obtain uniform System measures its fluorescence intensity F0；
(2) in the uniform system obtained by step (1), the solution for containing over cure acid ion to be measured is added, after being stirred to react, Measure its fluorescence intensity F；
(3) Y=(F is calculated0- F)/F0, then by formula Y=0.526 of relationship between expression over cure acid ion and fluorescence intensity ×logC(S2O8 2-)+3.044, R=0.955, obtain persulfuric acid ion concentration.
In step (1), S is being added2O8 2-Conjugated polyelectrolytes-Nano silver piece system fluorescence intensity is measured before ion, S is added2O8 2-After ion, the fluorescence in the system is quenched, by the variation of detection fluorescence, then by testing different S2O8 2-From Fluorescence intensity level under sub- concentration obtains the formula of relationship between expression over cure acid ion and fluorescence intensity, finally calculates S2O8 2-Ion concentration.
Preferably, in step (1), the conjugated polyelectrolytes are polyfluorene class, and positively charged hair blue-fluorescence contains pyridyl group Group, has the characteristics that water-soluble.
Preferably, in step (1), the general formula of the chemical structure of the conjugated polyelectrolytes are as follows:
, wherein n is 86~258 In integer.The characteristics of conjugated polyelectrolytes, essentially consists in the blue light group contained by polyfluorene, there is conjugated polyelectrolytes The good characteristic of blue light-emitting, has a fluorescence signal enlarge-effect, and due to containing pyridine groups and outstanding conjugation coordinating group, Allow the conjugated polyelectrolytes and silver nano material effectively compound, and pyridine also has good water solubility, so that altogether Yoke polyelectrolyte is soluble easily in water, is suitable for wide range.
Preferably, the synthetic method of the conjugated polyelectrolytes, comprising the following steps:
1) by after the mixed solution deoxygenation of water, dimethylformamide and diisopropylamine, under nitrogen protection, 2,7- bis- is added Iodo- 9,9- bis- (6'- (N, N, N- trimethyl ammonium)-hexyl) bromine fluorenes, 2,6- diacetylene pyridine, tetra-triphenylphosphine palladium and CuI, Heating reaction to solution is in brown color, is cooled to room temperature, centrifugation removal insoluble matter, filtrate spin concentration；
2) concentrate obtained by step 1) is instilled in the acetone-diethyl ether mixed liquor of stirring, is stood, remove supernatant liquor, under Layer carries out centrifugal treating, repeats aforementioned operation >=1 time, is dried in vacuo,.
Preferably, in step 1), the volume ratio of the water, dimethylformamide and diisopropylamine be 1.5~2.5:2~ 4: 1.Water is more advantageous to the formation of water-soluble polymer under the ratio.
Preferably, in step 1), the time of the deoxygenation is 5~15 min.
Preferably, in step 1), 2,7- bis- iodo- 9,9- bis- (6'- (N, N, N- trimethyl ammonium)-hexyl) bromine fluorenes, 2,6- The molar ratio of diacetylene pyridine, tetra-triphenylphosphine palladium and CuI is 8~15:8~15:1:1, the total mole number of the raw material Molal volume ratio with water, dimethylformamide and diisopropylamine total volume is 0.005~0.030 mol/L.Described 43 The content of Phenylphosphine palladium and CuI are higher, then react faster, if but too high levels, it will be unfavorable for forming required uniform polymerization degree Polymer.
Preferably, in step 1), the temperature of the heating reaction is 40~60 DEG C, and the time is 12~40 h.Excessively high temperature Degree and too long time are all difficult to obtain the polyelectrolyte of suitable molecular weight size.
Preferably, in step 2, the mass ratio of concentrate and acetone-diethyl ether mixed liquor described in step 2 obtained by step 1) is More preferable 1.0~the 1.5:100 of 0.8~3.0:100().Using acetone-diethyl ether mixed liquor dissolved impurity, be conducive to electrolyte Separation.
Preferably, in step 2, the volume ratio of acetone and ether is 1.2~1.8:1 in the acetone-diethyl ether mixed liquor.
Preferably, in step 2, the speed of the instillation is 0.5~1.0 mL/min.The excessive velocities of dropwise addition are excessively slow, All it is unfavorable for the steady progress of reaction.
Preferably, in step 2, the speed of the stirring is 400~700 r/min.Revolving speed is too fast or too slow to be unfavorable for Sufficiently reaction.
Preferably, in step 1), iodo- 9,9- bis- (6'- (N, N, N- trimethyl ammonium)-hexyl) the bromine fluorenes of 2, the 7- bis- Synthetic method be: in iodo- 9,9- bis- (the 6'- bromine hexyl) fluorenes of 2,7- bis- with mass ratio 1:35~45:40~55 be added three Methylamine and tetrahydrofuran are heated to reflux 2~4 d at 40~60 DEG C, after evaporated under reduced pressure, are washed with ether solid to get white Body product.
Preferably, the synthetic method of iodo- 9,9- bis- (the 6'- bromine hexyl) fluorenes of 2, the 7- bis- is: by mass concentration 40~ After 60% potassium hydroxide aqueous solution stirring is warming up to 70~80 DEG C, 2,7- that mass ratio is 5~10:1:30~40 are added Diiodo- fluorenes, tetrabutylammonium bromide and 1,6- dibromo-hexane, the quality of the potassium hydroxide are 2,7- diiodo- fluorenes, tetrabutyl phosphonium bromide Ammonium and 1, after 10~20 min of insulation reaction, is rapidly cooled to room temperature, uses dichloro by 15~20 times of 6- dibromo-hexane gross mass Methane extracts >=2 times, merges organic layer, respectively successively with the aqueous hydrochloric acid solution of 0.5~1.5 mol/L, water and 0.5~1.5 The NaCl aqueous solution of mol/L washs >=1 time, then uses anhydrous Na2SO4It dries, filters, evaporated under reduced pressure, then product silica gel will be evaporated Column chromatography, and with n-hexane: the mixed liquor that the volume ratio of chloroform is 8~10:1 elutes, and eluent evaporated under reduced pressure is to get pale yellow Color crystalline product.Excessive potassium hydroxide be conducive to keep compared with strong basicity environment in favor of obtain purity is high target product.
Preferably, the synthetic method of 2, the 7- diiodo- fluorenes is: by CH3COOH: H2O: H2SO4Volume ratio be 25~ The mixed liquor stirring of 35:1~5:1 is warming up to 70~90 DEG C, then with mixed liquor: fluorenes: KIO3: I2=60~120:2:1~ Fluorenes, KIO is added in the mass ratio of 2:1~43And I2, after reacting 8~12 h, solution colour is yellow by brown stain, is stopped anti- Should and it is cooling, filter, collect precipitating, successively use the Na of water and 1.5~2.5 mol/L respectively2CO3Solution washing is precipitated to filtrate It is in neutrality, with recrystallize with dichloromethane to get product as light yellow solid.
Preferably, in step 1), the synthetic method of the tetra-triphenylphosphine palladium is: by PdCl2, triphenylphosphine and dimethyl Sulfoxide is with the mixing of mass ratio 1:5~10:50~150, and under nitrogen protection, stirring is warming up to 140~160 DEG C, insulation reaction 12 After~18 min, solution colour is reddened by yellow, then with 0.5~1.0 mL/min of speed, with hydrazine hydrate and dimethyl sulfoxide Mass ratio is that 1:60~100 instills hydrazine hydrate, is stood, and cooling, filtering, filter residue is washed >=4 times with ethyl alcohol, and ether washs >=2 times, .
Preferably, in step 1), the synthetic method of 2, the 6- diacetylene pyridine is: by the tetra-triphenylphosphine palladium, CuI and 2,6- dibromo pyridine are with the mixing of 6~10:1:20 of mass ratio~50, under nitrogen protection, with above-mentioned mixed raw material and first Benzene-diisopropylamine mixed solution mass ratio is 1:6~18, and toluene is added: the volume ratio of diisopropylamine is the first of 3~5:1 Benzene-diisopropylamine mixed solution, then with 0.5~1.0mL/min speed, toluene-diisopropylamine mixed solution and trimethyl silicane The mass ratio of ethyl-acetylene is 10~15:1, and trimethyl silicane ethyl-acetylene is added and is filtered to remove not after reacting 10~15 h under room temperature Molten object, then using petroleum ether: the mixed solution that the volume ratio of methylene chloride is 4~6:1 is as solvent, with silica gel column chromatography point From obtaining pure intermediate products, then at normal temperature, pure intermediate products be dissolved in tetrahydro with 1:60~90 mass volume ratio (g/mL) Furans: the volume ratio of methanol is the in the mixed solvent of 1:0.8~1.2, mixed solvent and K2CO3Mass ratio be 1~10:1 add Enter K2CO3, stir 10~15 h, filtering, filtrate is concentrated, then with petroleum ether: the volume ratio of methylene chloride is the mixing of 1~2:1 Solution is separated as solvent with silica gel column chromatography,.
Preferably, in step (1), the nano silver is one of Nano silver piece, silver nanowires or Nano silver grain etc. Or it is several.
Preferably, the partial size of the Nano silver piece and Nano silver grain, silver nanowires diameter≤50 nm.
Preferably, the Nano silver piece solution the preparation method comprises the following steps: under the conditions of room temperature is protected from light, in silver nitrate solution plus Enter citric acid three sodium solution, polyvinylpyrrolidonesolution solution and hydrogenperoxide steam generator, it is disposable quickly to add after being mixed evenly Enter sodium borohydride solution, is quickly stirred to react 20~40 min, which deepens Huang by yellow, darkviolet is eventually become,. Nano silver piece solution deepens Huang during the preparation process, by yellow, eventually becomes darkviolet, after being measured with ultraviolet specrophotometer, Wavelength is in 551 nm or so；By gained Nano silver piece solution under the conditions of being protected from light for 4 DEG C, the storage several months is still stable.
Preferably, the mass ratio of the silver nitrate, trisodium citrate, polyvinylpyrrolidone and hydrogenperoxide steam generator is 1: 30~25:65~80:150~180.It, can be dense by adjusting its by addition polyvinylpyrrolidone as surfactant The pattern and color that degree effectively control Nano silver piece is formed, increase its stability.
Preferably, 0.01~1.00 mmol/L(of molar concentration more preferable 0.05~0.5 of the silver nitrate solution Mmol/L), more preferable 20~40 mmol/L of 10~50 mmol/L(of molar concentration of the citric acid three sodium solution), it is described poly- More preferable 0.3~0.9 mmol/L of 0.1~1.0 mmol/L(of molar concentration of vinylpyrrolidone solution), the hydrogen peroxide The mass fraction of solution is 10~30%.
Preferably, more preferable 80~150 mmol/ of 50~200 mmol/L(of molar concentration of the sodium borohydride solution L), the concentration after the sodium borohydride is added in mixed solution is more preferable 0.6~1.5 mmol/ of 0.5~2.0 mmol/L( L).Sodium borohydride addition excessively is not easy to form triangular silver nanosheet, and solution colour easily deepens.
Preferably, in step (1), the molar ratio of the conjugated polyelectrolytes and nano silver is that 1:0.5~2.0(is more preferable 1:0.6~1.0).Since nano silver material has certain quenching effect to conjugated polymer, when the conjugated polymer of addition with receive When the ratio of meter Yin >=1, better effect.
Preferably, in step (1), the sum of conjugated polyelectrolytes aqueous solution and Nano silver solution and the volume ratio of buffer are 10~40:100.The volume of buffer reaches the validity that matched uniform system total volume half more can guarantee buffer system.
Preferably, in step (1), the dosage of water is so that concentration of the conjugated polyelectrolytes in uniform system is 2 ×10-6~2 × 10-5 Mol/L(more preferable 3 × 10-6~1.5 × 10-5Mol/L, still more preferably 4 × 10-6~1 × 10- 5Mol/L), concentration of the nano silver in uniform system is 2 × 10-6~2 × 10-5 Mol/L(more preferable 2.2 × 10-6~ 1.5×10-5Mol/L, still more preferably 2.5 × 10-6~1 × 10-5 Mol/L).Efficiency is quenched with addition conjugated polymer The increase of concentration and increase, after tend towards stability；The concentration of nano silver is excessive, then makes the reduction of fluorescent quenching efficiency, nano silver Concentration is too small, then cannot significantly be etched by over cure acid ion.
It is highly preferred that the concentration of the conjugated polyelectrolytes aqueous solution is 0.5 × 10-4~1.5 × 10-4 Mol/L, it is described The concentration of Nano silver solution is 0.5 × 10-4~1.5 × 10-4mol/L。
Preferably, in step (1), the buffer is that hydrogen is added in the mixed acid aqueous solution of 0.03~0.05 mol/L For sodium oxide molybdena to pH=3~10, the mixed acid is that phosphoric acid, boric acid and acetic acid are mixed with mass ratio 1:1~3:1~3.
Preferably, in step (1), the time being stirred to react is 8~12 min.
Preferably, in step (2), the time being stirred to react is 20~40 min.
In step (3), with (F0- F)/F0As unified reference point, the intensity of fluorescent quenching is represented, the value is bigger, explanation Quenching is more obvious, and indicates the S detected2O8 2-Ion concentration is higher.In the formula,C(S2O8 2-) unit be mol/L.
The detection mechanism of the method for the present invention is: conjugated polyelectrolytes have both the photoelectric property and electrolyte of conjugated polymer The sensitivity of detection can be improved in water solubility, and Nano silver piece has good extinction coefficient, and conjugated polyelectrolytes are to Nano silver piece There is good peptizaiton, by S2O8 2-Ion is added in conjugated polyelectrolytes-Nano silver piece buffer solution, shows it Strong oxidizing property carries out oxide etch to the system, realizes S by detection fluorescent quenching2O8 2-The detection of ion.
Nitrogen used in the present invention is the high pure nitrogen of purity >=99.9%.
The method of the present invention has the beneficial effect that:
Detection method constitutes new nano complex dexterously by Nano silver piece in conjunction with conjugated polyelectrolytes System, hence it is evident that the sensitivity of persulfate detection is improved, it is simple and easy, accurate, rapid, highly sensitive, lowest detection is limited to 9 × 10-7 Mol/L, and 1 × 10-6~9 × 10-5Detection is linear good in the range of mol/L, is showed intuitively with fluorescence spectrum, should Method choice is good, suitable for the detection in the case of more ion interference.
Detailed description of the invention
Fig. 1 is selective histogram of 3 conjugated polyelectrolytes of the embodiment-Nano silver piece system (pH=5) to different ions；
Fig. 2 is 3 conjugated polyelectrolytes of embodiment-Nano silver piece system to various concentration S2O8 2-Fluorescence response figure；
Fig. 3 is 3 conjugated polyelectrolytes of embodiment-Nano silver piece system to various concentration S2O8 2-Fluorescence response linear graph；
Fig. 4 is conjugated polyelectrolytes dosages different in conjugated polyelectrolytes-Nano silver piece system to S2O8 2-Fluorescence response (Examples 1 to 5 is the 4th~8 point from left to right to figure；In figure,C P1Indicate conjugated polyelectrolytes uniform system obtained by step (1) In concentration)；
Fig. 5 is Nano silver piece dosages different in conjugated polyelectrolytes-Nano silver piece system to S2O8 2-Fluorescence response figure (embodiment 6~9 is the 1st~4 point from left to right；In figure,C AgNPRsIndicate Nano silver piece in the uniform system obtained by step (1) Concentration)；
Fig. 6 is the differential responses time in conjugated polyelectrolytes-Nano silver piece system to S2O8 2-Fluorescence response figure (implement Example 10~14 is the 9th~13 point from left to right)；
Fig. 7 is the monodispersed conjugated polyelectrolytes of embodiment 3-Nano silver piece electron microscope；
Fig. 8 is that S is added in the monodispersed conjugated polyelectrolytes of embodiment 3-Nano silver piece2O8 2-Electron microscope afterwards.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Nitrogen used in the embodiment of the present invention is the high pure nitrogen of purity >=99.9%；The embodiment of the present invention is used Chemical reagent obtained unless otherwise specified by routine business approach.
Conjugated polyelectrolytes reference example 1
Its general formula of the chemical structure are as follows:
, wherein n is 86~110；It should Conjugated polyelectrolytes are polyfluorene class, and positively charged hair blue-fluorescence contains pyridine groups, has the characteristics that water-soluble.
Conjugated polyelectrolytes reference example 2
Its general formula of the chemical structure are as follows:
, wherein n is 160~190； The conjugated polyelectrolytes are polyfluorene class, and positively charged hair blue-fluorescence contains pyridine groups, has the characteristics that water-soluble.
Conjugated polyelectrolytes reference example 3
Its general formula of the chemical structure are as follows:
, wherein n is 230~258； The conjugated polyelectrolytes are polyfluorene class, and positively charged hair blue-fluorescence contains pyridine groups, has the characteristics that water-soluble.
The synthetic method reference example 4 of two iodo- 9,9- bis- (6'- (N, N, N- trimethyl ammonium)-hexyl) bromine fluorenes
5 mL(3.3 g are added in iodo- 9,9- bis- (the 6'- bromine hexyl) fluorenes of 0.0900 g 2,7- bis-) trimethylamine and 5 mL (4.45 g) tetrahydrofuran is heated to reflux 3 d at 50 DEG C, after evaporated under reduced pressure, is washed with ether to get white solid product 0.0621 g, 60 % of yield.
The synthetic method of iodo- 9,9- bis- (the 6'- bromine hexyl) fluorenes of the 2,7- bis- is: by the hydrogen of 30 g mass concentrations 50% After oxidation aqueous solutions of potassium stirring is warming up to 75 DEG C, 0.25 g(0.6 mmol is added) 2,7- diiodo- fluorenes, 0.0425 g(0.13 Mmol) tetrabutylammonium bromide and 1.5 g(6 mmol) 1,6- dibromo-hexane, after 15 min of insulation reaction, it is rapidly cooled to room Temperature is extracted with dichloromethane 3 times, merges organic layer, respectively successively with the aqueous hydrochloric acid solution of 1 mol/L, water and 1 mol/L NaCl aqueous solution washs 1 time, then uses anhydrous Na2SO4It dries, filters, evaporated under reduced pressure, then product silica gel column chromatography will be evaporated, and With n-hexane: the mixed liquor that the volume ratio of chloroform is 9:1 elutes, and eluent evaporated under reduced pressure is to get pale yellow crystals product 0.269 G, yield 60.5%.
The synthetic method of the 2,7- diiodo- fluorenes is: by 82.5 mL(86.625 g) CH3COOH, 6.6mL(6.6 g) H2O With 1.65mL(3.02 g) H2SO4Mixed liquor stirring be warming up to 80 DEG C, add 1.245 g(7.5 mmol) fluorenes, 0.64 g (3 mmol) KIO3With 2.05 g(8.1 mmol) I2, after reacting 10 h, solution colour is yellow by brown stain, stops reaction And it is cooling, it filters, collects precipitating, successively use the Na of water and 2 mol/L respectively2CO3Solution washing is precipitated to filtrate and is in neutrality, and uses Recrystallize with dichloromethane is to get 1.2871 g of product as light yellow solid, 41 % of yield.
Tetra-triphenylphosphine palladium reference example 5
By 0.8867 g(5 mmol) PdCl2, 6.5573 g(25 mmol) triphenylphosphine and 80 mL(88 g) dimethyl Sulfoxide mixing, under nitrogen protection, stirring is warming up to 150 DEG C, and after 15 min of insulation reaction, solution colour is reddened by yellow, then With 1 mL/min of speed, 0.97 mL(20 mmol is instilled, 1 g) hydrazine hydrate, standing, cooling is filtered, filter residue washes 5 with ethyl alcohol Secondary, ether washs 3 times,.
Diacetylene pyridine reference example 6
By 0.462 g(0.4 mmol) reference example, 5 gained tetra-triphenylphosphine palladium, 0.076 g(0.4 mmol) CuI and 1.90 G(8 mmol) mixing of 2,6- dibromo pyridine, under nitrogen protection, and 25 mL(20.989 g of addition) toluene: the volume of diisopropylamine Than the toluene for 4:1-diisopropylamine mixed solution, then with 1 mL/min speed, 2.27 mL(1.578 g are added) trimethyl Silicon substrate acetylene is filtered to remove insoluble matter, then after reacting 12 h under room temperature with petroleum ether: the volume ratio of methylene chloride is the mixed of 5:1 Solution is closed as solvent, is separated with silica gel column chromatography, obtains pure intermediate products, then at normal temperature, the pure intermediate products of 1.2 g are molten Solution is in 75 mL(63 g) tetrahydrofuran: the volume ratio of methanol is the in the mixed solvent of 1:1, and 14 g K are added2CO3, 12 h are stirred, Filtering, filtrate concentration, then using petroleum ether: the volume ratio of methylene chloride is the mixed solution of 1.5:1 as solvent, uses silicagel column Chromatography,.
The synthetic method reference example 7 of conjugated polyelectrolytes reference example 1
1) mixed solution of 2.5 mL water, 3.75 mL dimethylformamides and 1.3 mL diisopropylamines is led into nitrogen deoxygenation After 10 min, under nitrogen protection, 0.0647 g(0.075 mmol is added) iodo- 9,9-, the bis- (6'- of gained 2, the 7- bis- of reference example 4 (N, N, N- trimethyl ammonium)-hexyl) bromine fluorenes, 0.0094 g(0.074 mmol) 6 gained 2,6- diacetylene pyridine of reference example, 0.0087 g(7.5 μm of ol) reference example 5 gained tetra-triphenylphosphine palladium and 0.0015 g(7.5 μm of ol) CuI, 50 DEG C are heated to, 12 h are reacted, until solution is in brown color, are cooled to room temperature, centrifugation removal insoluble matter, filtrate spin concentration obtains 1.2 g of concentrate；
2) concentrate obtained by 1.2 g step 1) is stirred with 0.8 mL/min of speed, instillation with 500 r/min speed In 150 mL acetone-diethyl ether mixed liquors (acetone: the volume ratio of ether is 75:50,113.724g), stands, removes supernatant liquor, Lower layer carries out centrifugal treating, repeats aforementioned operation 2 times, vacuum drying,.
In deionized water by the dissolution of gained conjugated polyelectrolytes, with concentration 1 × 10-4Mol/L(is calculated with repetitive unit) As stock solution.
The synthetic method reference example 8 of conjugated polyelectrolytes reference example 2
1) mixed solution of 2.5 mL water, 3.75 mL dimethylformamides and 1.3 mL diisopropylamines is led into nitrogen deoxygenation 8 After min, under nitrogen protection, 0.0647 g(0.075 mmol is added) iodo- 9, the 9- of 2,7- of the gained of reference example 4 bis- bis- (6'- (N, N, N- trimethyl ammonium)-hexyl) bromine fluorenes, 0.0095 g(0.075 mmol) 6 gained 2,6- diacetylene pyridine of reference example, 0.0087 g(7.5 μm of ol) reference example 5 gained tetra-triphenylphosphine palladium and 0.0015 g(7.5 μm of ol) CuI, 50 DEG C are heated to, 24 h are reacted, until solution is in brown color, are cooled to room temperature, centrifugation removal insoluble matter, filtrate spin concentration obtains 1.8 g of concentrate；
2) concentrate obtained by 1.8 g step 1) is stirred with 0.6 mL/min of speed, instillation with 400 r/min speed 200 mL acetone-diethyl ether mixed liquors (acetone: the volume ratio of ether be 75:50,151.632 g) in, stand, removal upper layer it is clear Liquid, lower layer carry out centrifugal treating, repeat aforementioned operation 2 times, vacuum drying,.
In deionized water by the dissolution of gained conjugated polyelectrolytes, with concentration 1 × 10-4Mol/L(is calculated with repetitive unit) As stock solution.
The synthetic method reference example 9 of conjugated polyelectrolytes reference example 3
1) mixed solution of 2.5 mL water, 3.75 mL dimethylformamides and 1.3 mL diisopropylamines is led into nitrogen deoxygenation After 12 min, under nitrogen protection, 0.0647 g(0.075 mmol is added) iodo- 9,9-, the bis- (6'- of gained 2, the 7- bis- of reference example 4 (N, N, N- trimethyl ammonium)-hexyl) bromine fluorenes, 0.0098 g(0.077 mmol) 6 gained 2,6- diacetylene pyridine of reference example, 0.0087 g(7.5 μm of ol) reference example 5 gained tetra-triphenylphosphine palladium and 0.0015 g(7.5 μm of ol) CuI, 50 DEG C are heated to, 36 h are reacted, until solution is in dark-brown, are cooled to room temperature, centrifugation removal insoluble matter, filtrate spin concentration obtains 2.4 g of concentrate；
2) concentrate obtained by 2.4 g step 1) is instilled into 250 stirred with 700 r/min speed with 1 mL/min of speed ML acetone-diethyl ether mixed liquor (acetone: the volume ratio of ether be 75:50,189.54 g) in, stand, remove supernatant liquor, lower layer Centrifugal treating is carried out, is repeated aforementioned operation 2 times, vacuum drying,.
In deionized water by the dissolution of gained conjugated polyelectrolytes, with concentration 1 × 10-4Mol/L(is calculated with repetitive unit) As stock solution.
The preparation method reference example 10 of Nano silver piece solution
Under the conditions of room temperature is protected from light, 1.5 mL, 30 mmol/L are added in 25 mL, the silver nitrate solution of 0.1 mmol/L Citric acid three sodium solution, 1.5 mL, 0.7 mmol/L(K-30, Mw~29000 g/mol) polyvinylpyrrolidonesolution solution and 60 Hydrogenperoxide steam generator (the quality of silver nitrate, trisodium citrate, polyvinylpyrrolidone and hydrogen peroxide of 30 % of μ L mass fraction Than after being mixed evenly, disposably rapidly joining 250 μ L, the sodium borohydride of 100 mmol/L for 1:31:72:160) Sodium borohydride solution is quickly stirred to react 30 min, which deepens Huang by yellow and eventually become darkviolet,.
Through detecting, the concentration of Nano silver piece is 1 × 10-4 Mol/L, partial size≤50 nm of Nano silver piece, uses ultraviolet spectrometry Wavelength is in 551 nm after photometer measurement.
The preparation method reference example 11 of buffer
It is in mixed acid (phosphoric acid, boric acid and acetic acid are mixed with mass ratio 1:1:1) aqueous solution of 0.04 mol/L Sodium hydroxide is added to pH=5.
A kind of conjugated polyelectrolytes-silver detection persulfuric acid ion concentration embodiment of the method 1~5
(1) respectively by 30 μ L, 40 μ L, 50 μ L, 60 μ L, 70 μ L, 1 × 10-4The conjugated polyelectrolytes reference example 1 of mol/L Aqueous solution and 50 μ L, 1 × 10-410 gained Nano silver piece solution of mol/L reference example and 500 μ L reference example, 11 gained buffer are molten Yu Shuizhong adds water to be settled to 1 mL, after being stirred to react 10 min, respectively uniform system 1~5, measure its fluorescence intensity respectively F0；
(2) respectively in the uniform system 1~5 obtained by step (1), the solution (reason containing over cure acid ion to be measured is added It is 9 × 10 by concentration-5Mol/L), after being stirred to react 30 min, its fluorescence intensity F is measured respectively；
(3) Y=(F is calculated separately to obtain0- F)/F0=0.877,0.898,0.912,0.913,0.912, then by expression persulfuric acid Formula Y=0.526 × log of relationship between radical ion and fluorescence intensityC(S2O8 2-)+3.044, R=0.955, over cure is obtained respectively Acid ion concentration=7.58 × 10-5, 8.3 × 10-5, 8.91 × 10-5, 8.92 × 10-5, 8.91 × 10-5 mol/L。
As shown in Figure 1, different anions are for (the i.e. poly- electrolysis of conjugation of uniform system obtained by 3 step of the embodiment of the present invention (1) Matter-Nano silver piece system, similarly hereinafter) there is different responses, but far below to S2O8 2-Influence, illustrate the method for the present invention walk Suddenly uniform system obtained by (1) is for S2O8 2-There is good selectivity.
As shown in Fig. 2, illustrating that uniform system is to various concentration S obtained by 3 step of the embodiment of the present invention (1)2O8 2-Fluorescence tool There is more apparent response difference.
As shown in figure 3, being uniform system obtained by 3 step of the embodiment of the present invention (1) to various concentration S2O8 2-Fluorescence response Linear graph, and in this, as the calculation formula of step (3), it calculates and contains S2O8 2-The unknown concentration of solution.
As shown in figure 4, for Y=(F obtained by 1~5 step of the embodiment of the present invention (3)0- F)/F0Curve graph the (from left to right the 4th ~8 points), it follows that in the conjugated polyelectrolytes in the concentration range in system, with conjugated polyelectrolytes dosage Increase, (F0- F)/F0Value is bigger, when conjugated polyelectrolytes dosage is 50 μ L, (F0- F)/F0Value tends towards stability, and substitution Y= 0.526×logC(S2O8 2-) formula of+3.044, R=0.955 can calculate persulfuric acid ion concentration.
As shown in Figure 7,8, by comparing in uniform system obtained by 3 step of the embodiment of the present invention (1), monodispersed conjugation is poly- S is added in electrolyte-Nano silver piece2O8 2-S is added in the Electronic Speculum graph discovery of front and back2O8 2-Afterwards, conjugated polyelectrolytes-Nano silver piece system It is oxidized etching, so that the fluorescence of conjugated polyelectrolytes quenches, detection S is reached with this2O8 2-Purpose；In Fig. 7, Particle, that is, nanometer sheet of triangle, partial size≤50 nm.
A kind of conjugated polyelectrolytes-silver detection persulfuric acid ion concentration embodiment of the method 6~9
(1) by 50 μ L, 1 × 10-4The aqueous solution of the conjugated polyelectrolytes reference example 2 of mol/L, respectively with 25 μ L, 50 μ L, 75 μ L, 100 μ L, 1 × 10-410 gained Nano silver piece solution of mol/L reference example and 500 μ L reference example, 11 gained buffer are dissolved in In water, water is added to be settled to 1 mL, after being stirred to react 10 min, respectively uniform system 6~9, measure its fluorescence intensity F respectively0；
(2) respectively in the uniform system 6~9 obtained by step (1), the solution (reason containing over cure acid ion to be measured is added It is 8 × 10 by concentration-5Mol/L), after being stirred to react 30 min, its fluorescence intensity F is measured respectively；
(3) Y=(F is calculated separately to obtain0- F)/F0=0.842,0.876,0.856,0.839, then by expression over cure acid ion Formula Y=0.526 × log of relationship between fluorescence intensityC(S2O8 2-)+3.044, R=0.955, respectively over cure acid group from Sub- concentration=6.46 × 10-5, 7.58 × 10-5, 6.92 × 10-5, 6.42 × 10-5 mol/L。
As shown in figure 5, for Y=(F obtained by 6~9 step of the embodiment of the present invention (3)0- F)/F0Curve graph the (from left to right the 1st ~4 points), it follows that in the Nano silver piece in the concentration range in system, with the increase of Nano silver piece dosage, (F0- F)/F0It is worth first increases and then decreases, when the dosage of Nano silver piece is 50 μ L, fluorescent quenching intensity is best, substitutes into Y=0.526 ×logC(S2O8 2-) formula of+3.044, R=0.955 can calculate persulfuric acid ion concentration.
A kind of conjugated polyelectrolytes-silver detection persulfuric acid ion concentration embodiment of the method 10~14
(1) by 250 μ L, 1 × 10-4The aqueous solution of the conjugated polyelectrolytes reference example 3 of mol/L, and 250 μ L, 1 × 10-4 10 gained Nano silver piece solution of mol/L reference example and 2500 μ L reference example, 11 gained buffer are soluble in water, and water is added to be settled to 5 ML after being stirred to react 10 min, is divided into 5 parts, respectively uniform system 10~14, measure its fluorescence intensity F respectively0；
(2) solution for containing over cure acid ion to be measured is added in the uniform system 10~14 obtained by step (1) respectively (theoretical concentration is 6 × 10-5Mol/L), it is stirred to react respectively, 20 min, 25 min, 30 min, 35 min, after 40 min, point Its fluorescence intensity F is not measured；
(3) Y=(F is calculated separately to obtain0- F)/F0=0.772,0.781,0.797,0.803,0.799, then by expression persulfuric acid Formula Y=0.526 × log of relationship between radical ion and fluorescence intensityC(S2O8 2-)+3.044, R=0.955, over cure is obtained respectively Acid ion concentration=4.79 × 10-5, 5.01 × 10-5, 5.35 × 10-5, 5.62 × 10-5, 5.39 × 10-5 mol/L。
As shown in fig. 6, for Y=(F obtained by 10~14 step of the embodiment of the present invention (3)0- F)/F0Curve graph (from left to right 9th~13 point), it follows that with the increase in reaction time, (F0- F)/F0Value gradually increases, glimmering when the time is 30 min Optical quenching intensity is almost unchanged, substitutes into Y=0.526 × logC(S2O8 2-) formula of+3.044, R=0.955 can calculate over cure Acid ion concentration.

Claims (16)

1. a kind of conjugated polyelectrolytes-silver detection persulfuric acid ion concentration method, which is characterized in that including following step It is rapid:
(1) conjugated polyelectrolytes aqueous solution, Nano silver solution and buffer is soluble in water, after being stirred to react, uniform system is obtained, Measure its fluorescence intensity F0；
The general formula of the chemical structure of the conjugated polyelectrolytes are as follows:
,
Wherein, n is the integer in 86~258；
(2) in the uniform system obtained by step (1), the solution for containing over cure acid ion to be measured is added, after being stirred to react, measurement Its fluorescence intensity F；
(3) Y=(F is calculated0- F)/F0, then by relationship between expression over cure acid ion and fluorescence intensity formula Y=0.526 × logC(S2O8 2-)+3.044, R=0.955, obtain persulfuric acid ion concentration.
2. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 1, feature exist In: in step (1), the conjugated polyelectrolytes are polyfluorene class, and positively charged hair blue-fluorescence contains pyridine groups, are had water-soluble The characteristics of property.
3. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 1, feature exist In the synthetic method of the conjugated polyelectrolytes, comprising the following steps:
1) by after the mixed solution deoxygenation of water, dimethylformamide and diisopropylamine, under nitrogen protection, it is iodo- that 2,7- bis- is added 9,9- bis- (6'- (N, N, N- trimethyl ammonium)-hexyl) bromine fluorenes, 2,6- diacetylene pyridine, tetra-triphenylphosphine palladium and CuI, add Thermal response to solution is in brown color, is cooled to room temperature, centrifugation removal insoluble matter, filtrate spin concentration；
2) concentrate obtained by step 1) is instilled in the acetone-diethyl ether mixed liquor of stirring, is stood, remove supernatant liquor, lower layer into Row centrifugal treating repeats aforementioned operation >=1 time, is dried in vacuo,.
4. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 3, feature exist In: in step 1), the volume ratio of the water, dimethylformamide and diisopropylamine is 1.5~2.5:2~4:1；Step 1) In, the time of the deoxygenation is 5~15 min；In step 1), 2,7- bis- iodo- 9,9-, bis- (6'- (N, N, N- trimethyl ammonium)- Hexyl) bromine fluorenes, 2,6- diacetylene pyridine, tetra-triphenylphosphine palladium and CuI molar ratio be 8~15:8~15:1:1, raw material Total mole number and water, dimethylformamide and diisopropylamine total volume molal volume ratio be 0.005~0.030 mol/ L；In step 1), the temperature of the heating reaction is 40~60 DEG C, and the time is 12~40 h；It is dense obtained by step 1) in step 2 The mass ratio of acetone-diethyl ether mixed liquor described in contracting object and step 2 is 0.8~3.0:100；In step 2, the acetone-diethyl ether The volume ratio of acetone and ether is 1.2~1.8:1 in mixed liquor；In step 2, the speed of the instillation is 0.5~1.0 mL/ min；In step 2, the speed of the stirring is 400~700 r/min.
5. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver described according to claim 1~one of 4, Be characterized in that: in step (1), the nano silver is one or more of Nano silver piece, silver nanowires or Nano silver grain；Institute State the partial size of Nano silver piece and Nano silver grain, diameter≤50 nm of silver nanowires.
6. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 5, feature exist In: the Nano silver piece solution the preparation method comprises the following steps: under the conditions of room temperature is protected from light, trisodium citrate is added in silver nitrate solution After being mixed evenly, it is molten disposably to rapidly join sodium borohydride for solution, polyvinylpyrrolidonesolution solution and hydrogenperoxide steam generator Liquid is quickly stirred to react 20~40 min, which deepens Huang by yellow, eventually becomes darkviolet,.
7. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 6, feature exist In the mass ratio of: the silver nitrate, trisodium citrate, polyvinylpyrrolidone and hydrogenperoxide steam generator be 1:30~25:65 ~80:150~180；0.01~1.00 mmol/L of molar concentration of the silver nitrate solution, the citric acid three sodium solution 10~50 mmol/L of molar concentration, 0.1~1.0 mmol/L of molar concentration of the polyvinylpyrrolidonesolution solution, the mistake The mass fraction of hydrogen peroxide solution is 10~30%；50~200 mmol/L of molar concentration of the sodium borohydride solution, the boron Concentration after sodium hydride addition in mixed solution is 0.5~2.0 mmol/L.
8. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver described according to claim 1~one of 4, Be characterized in that: in step (1), the molar ratio of the conjugated polyelectrolytes and nano silver is 1:0.5~2.0；Conjugated polyelectrolytes The volume ratio of the sum of aqueous solution and Nano silver solution and buffer is 10~40:100；The dosage of water is so that the conjugation is poly- Concentration of the electrolyte in uniform system is 2 × 10-6~2 × 10-5 Mol/L, concentration of the nano silver in uniform system are 2×10-6~2 × 10-5 mol/L；The buffer is that hydroxide is added in the mixed acid aqueous solution of 0.03~0.05 mol/L For sodium to pH=3~10, the mixed acid is that phosphoric acid, boric acid and acetic acid are mixed with mass ratio 1:1~3:1~3.
9. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 5, feature exist In: in step (1), the molar ratio of the conjugated polyelectrolytes and nano silver is 1:0.5~2.0；Conjugated polyelectrolytes aqueous solution Volume ratio with the sum of Nano silver solution and buffer is 10~40:100；The dosage of water is so that the conjugated polyelectrolytes Concentration in uniform system is 2 × 10-6~2 × 10-5 Mol/L, concentration of the nano silver in uniform system are 2 × 10-6~2 × 10-5 mol/L；The buffer is that sodium hydroxide is added extremely in the mixed acid aqueous solution of 0.03~0.05 mol/L PH=3~10, the mixed acid are that phosphoric acid, boric acid and acetic acid are mixed with mass ratio 1:1~3:1~3.
10. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 6, feature exist In: in step (1), the molar ratio of the conjugated polyelectrolytes and nano silver is 1:0.5~2.0；Conjugated polyelectrolytes aqueous solution Volume ratio with the sum of Nano silver solution and buffer is 10~40:100；The dosage of water is so that the conjugated polyelectrolytes Concentration in uniform system is 2 × 10-6~2 × 10-5 Mol/L, concentration of the nano silver in uniform system are 2 × 10-6~2 × 10-5 mol/L；The buffer is that sodium hydroxide is added extremely in the mixed acid aqueous solution of 0.03~0.05 mol/L PH=3~10, the mixed acid are that phosphoric acid, boric acid and acetic acid are mixed with mass ratio 1:1~3:1~3.
11. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 7, feature exist In: in step (1), the molar ratio of the conjugated polyelectrolytes and nano silver is 1:0.5~2.0；Conjugated polyelectrolytes aqueous solution Volume ratio with the sum of Nano silver solution and buffer is 10~40:100；The dosage of water is so that the conjugated polyelectrolytes Concentration in uniform system is 2 × 10-6~2 × 10-5 Mol/L, concentration of the nano silver in uniform system are 2 × 10-6~2 × 10-5 mol/L；The buffer is that sodium hydroxide is added extremely in the mixed acid aqueous solution of 0.03~0.05 mol/L PH=3~10, the mixed acid are that phosphoric acid, boric acid and acetic acid are mixed with mass ratio 1:1~3:1~3.
12. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver described according to claim 1~one of 4, Be characterized in that: in step (1), the time being stirred to react is 8~12 min；In step (2), the time being stirred to react For 20~40 min.
13. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 5, feature exist In: in step (1), the time being stirred to react is 8~12 min；In step (2), the time being stirred to react be 20~ 40 min。
14. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 6, feature exist In: in step (1), the time being stirred to react is 8~12 min；In step (2), the time being stirred to react be 20~ 40 min。
15. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 7, feature exist In: in step (1), the time being stirred to react is 8~12 min；In step (2), the time being stirred to react be 20~ 40 min。
16. the method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver according to claim 8, feature exist In: in step (1), the time being stirred to react is 8~12 min；In step (2), the time being stirred to react be 20~ 40 min。
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