CN108279224A - A method of detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver - Google Patents
A method of detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver Download PDFInfo
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Abstract
A method of persulfuric acid ion concentration being detected with conjugated polyelectrolytes silver, is included the following steps：（1）Conjugated polyelectrolytes aqueous solution, Nano silver solution and buffer solution is soluble in water, after being stirred to react, uniform system is obtained, measures its fluorescence intensity F0；（2）In step（1）In the uniform system of gained, the solution containing over cure acid ion to be measured is added, after being stirred to react, measures its fluorescence intensity F；（3）Calculating Y=（F0‑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 practicable, 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
Technical field
The present invention relates to a kind of methods of detection 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 technology
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
A kind of important raw and processed materials for bonding 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. were with Prussian blue（PB）The platinum disk electrode of modification detects over cure by voltammetry
The content of acid group, 5 × 10-5~3 × 10-3Have within the scope of M preferable linear（Microchem. J., 2000, 64,
155-159）；2003, F. De Oliveira etc. were noted 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. made persulfate be reacted rapidly with methylene blue by microwave activation, realizes 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 detects, and this method has good linear relationship, detection to be limited to 1 × 10 in 0.1~0.7 mM-5M（Anal. Methods,
2016, 8, 1483-1488）.But above technical process is cumbersome, higher to equipment requirement, analytic process is time-consuming and laborious,
Sensitivity for analysis is not high, and the actual production and monitoring for being unfavorable for the usually persulfate containing low concentration are applied.
Fluoroscopic examination 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
Thiosulfuric acid radical ion（CN106770103A）Deng detection, 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 has patent report and is used for fluorine ion（CN105295009A）, copper ion（CN101824139A）、
ATP（CN105348493A）And BSA（CN103588960A）Etc. biomolecule and cell（CN105348493A）Deng detection, but
It is that most conjugated polymer probe can only be dissolved in organic solvent, and water-soluble poor, building-up process is cumbersome time-consuming.
Invention content
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 practicable, accurate, rapid, highly sensitive, and lowest detection is limited to 9 × 10-7 Mol/L, and detect linear good poly- with conjugation
The method of electrolyte-silver detection persulfuric acid ion concentration.
The technical solution adopted by the present invention to solve the technical problems is as follows：It is a kind of to be detected with conjugated polyelectrolytes-silver
The method of sulfate ion concentration, includes the following steps：
（1）Conjugated polyelectrolytes aqueous solution, Nano silver solution and buffer solution is soluble in water, after being stirred to react, uniform system is obtained,
Measure its fluorescence intensity F0；
（2）In step（1）In the uniform system of gained, the solution containing over cure acid ion to be measured is added, after being stirred to react, measures
Its fluorescence intensity F；
（3）Calculating Y=（F0-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.
Step（1）In, S is being added2O8 2-The fluorescence intensity of conjugated polyelectrolytes-Nano silver piece system is measured before ion,
S is added2O8 2-After ion, the fluorescence in the system is quenched, and by the variation of detection fluorescence, then is passed through and is tested 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, step（1）In, the conjugated polyelectrolytes are polyfluorene class, and positively charged hair blue-fluorescence contains pyridyl group
Group, has the characteristics that water-soluble.
Preferably, step（1）In, the chemical structure of general formula of the conjugated polyelectrolytes is：
, wherein during n is 86~258
Integer.The characteristics of conjugated polyelectrolytes, essentially consists in the blue light group contained by polyfluorene, so that conjugated polyelectrolytes is had and turns blue
The good characteristic of light has fluorescence signal enlarge-effect, and due to containing pyridine groups and outstanding conjugation coordinating group so that
The conjugated polyelectrolytes can be effectively compound with silver nano material, and pyridine also has good water solubility so that conjugation is poly-
Electrolyte is soluble easily in water, is suitable for wide range.
Preferably, the synthetic method of the conjugated polyelectrolytes, includes the following steps：
1）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- diacetylenes 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）By step 1）Gained concentrate instill stirring acetone-diethyl ether mixed liquor in, stand, remove supernatant liquor, lower layer into
Row centrifugal treating repeats aforementioned operation >=1 time, is dried in vacuo,.
Preferably, step 1）In, the volume ratio of the water, dimethylformamide and diisopropylamine is 1.5~2.5:2~
4: 1.Water is more advantageous to the formation of water-soluble polymer under the ratio.
Preferably, step 1）In, the time of the deoxygenation is 5~15 min.
Preferably, step 1）In, 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, step 1）In, the temperature of the heating reaction is 40~60 DEG C, and the time is 12~40 h.Excessively high temperature
Degree and long time are all difficult to obtain the polyelectrolyte of suitable molecular weight size.
Preferably, step 2）In, step 1）Gained concentrate and step 2）The mass ratio of the acetone-diethyl ether mixed liquor is
0.8~3.0: 100（More preferable 1.0~1.5:100）.Using acetone-diethyl ether mixed liquor dissolved impurity, be conducive to electrolyte
Separation.
Preferably, step 2）In, the volume ratio of acetone and ether is 1.2~1.8 in the acetone-diethyl ether mixed liquor: 1.
Preferably, step 2）In, 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, step 2）In, the speed of the stirring is 400~700 r/min.Rotating speed is too fast or is unfavorable for slowly excessively
Fully reaction.
Preferably, step 1）In, 2, the 7- bis- iodo- 9,9- bis- (6'- (N, N, N- trimethyl ammonium)-hexyl) bromine fluorenes
Synthetic method be：With mass ratio 1 in 2,7- bis- iodo- 9,9- bis- (6'- bromines hexyl) fluorenes:35~45:40~55 are 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 2, the 7- bis- iodo- 9,9- bis- (6'- bromines hexyl) fluorenes is：By mass concentration 40~
After 60% potassium hydroxide aqueous solution stirring is warming up to 70~80 DEG C, it is 5~10 that mass ratio, which is added,: 1:30~40 2,7-
The quality of diiodo- fluorenes, tetrabutylammonium bromide and 1,6- dibromo-hexanes, the potassium hydroxide is 2,7- diiodo-s 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 masses
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 solutions of mol/L wash >=1 time, then use anhydrous Na2SO4It is dry, filtering, evaporated under reduced pressure, then product silica gel will be evaporated
Column chromatography, and with n-hexane:The volume ratio of chloroform is 8~10:1 mixed liquor elution, eluent evaporated under reduced pressure is to get pale yellow
Color crystalline product.Excessive potassium hydroxide is conducive to keep compared with strong basicity environment in favor of obtaining the high target product of purity.
Preferably, the synthetic method of 2, the 7- diiodo-s fluorenes is：By CH3COOH: H2O: H2SO4Volume ratio be 25~
35:1~5:1 mixed liquor stirring is warming up to 70~90 DEG C, then with mixed liquor:Fluorenes: KIO3: I2=60~120: 2:1~
2:Fluorenes, KIO is added in 1~4 mass ratio3And I2, after reacting 8~12 h, solution colour is yellow by brown stain, is stopped anti-
Should and it is cooling, filter, collect precipitation, use the Na of water and 1.5~2.5 mol/L successively respectively2CO3Solution washing is precipitated to filtrate
It is in neutrality, with recrystallize with dichloromethane to get product as light yellow solid.
Preferably, step 1）In, the synthetic method of the tetra-triphenylphosphine palladium is：By PdCl2, triphenylphosphine and dimethyl
Sulfoxide is with mass ratio 1:5~10:50~150 mixing, 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 (DMSO)
Mass ratio is 1:60~100 instill hydrazine hydrate, stand, cooling, and filtering, filter residue is washed >=4 times with ethyl alcohol, and ether washs >=2 times,
.
Preferably, step 1）In, the synthetic method of 2, the 6- diacetylenes pyridine is：By the tetra-triphenylphosphine palladium,
CuI and 2,6- dibromo pyridines are with mass ratio 6~10: 1:20~50 mixing, under nitrogen protection, with above-mentioned mixed raw material and first
The mass ratio of benzene-diisopropylamine mixed solution is 1:6~18, toluene is added:The volume ratio of diisopropylamine is 3~5:1 first
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, trimethyl silicane ethyl-acetylene is added and is filtered to remove not after reacting 10~15 h under room temperature
Molten object, then with petroleum ether:The volume ratio of dichloromethane is 4~6:1 mixed solution is as solvent, with silica gel column chromatography point
From pure intermediate products being obtained, then at normal temperatures, by pure intermediate products with mass volume ratio（g/mL）1:60~90 are dissolved in tetrahydrochysene
Furans:The volume ratio of methanol is 1:0.8~1.2 in the mixed solvent, mixed solvent and K2CO3Mass ratio be 1~10:1 adds
Enter K2CO3, 10~15 h, filtering are stirred, filtrate concentrates, then with petroleum ether:The volume ratio of dichloromethane is 1~2:1 mixing
Solution is detached as solvent with silica gel column chromatography,.
Preferably, step（1）In, the nano silver is one kind in Nano silver piece, nano silver wire or Nano silver grain etc.
Or it is several.
Preferably, diameter≤50 nm of the grain size of the Nano silver piece and Nano silver grain, nano silver wire.
Preferably, the preparation method of the Nano silver piece solution is：Under the conditions of room temperature is protected from light, add in silver nitrate solution
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 becomes deep yellow by yellow, eventually becomes darkviolet,.
Nano silver piece solution becomes deep yellow in 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 still stablizes.
Preferably, the mass ratio of the silver nitrate, trisodium citrate, polyvinylpyrrolidone and hydrogenperoxide steam generator is 1:
30~25:65~80:150~180.It is used as surfactant by the way that polyvinylpyrrolidone is added, it can be dense by adjusting its
The degree pattern that effectively control Nano silver piece is formed and color, increase its stability.
Preferably, 0.01~1.00 mmol/L of molar concentration of the silver nitrate solution（More preferable 0.05~0.5
mmol/L）, 10~50 mmol/L of molar concentration of the citric acid three sodium solution（More preferable 20~40 mmol/L）, described poly-
0.1~1.0 mmol/L of molar concentration of vinylpyrrolidone solution（More preferable 0.3~0.9 mmol/L）, the hydrogen peroxide
The mass fraction of solution is 10~30%.
Preferably, 50~200 mmol/L of molar concentration of the sodium borohydride solution（More preferable 80~150 mmol/
L）, a concentration of 0.5~2.0 mmol/L after the sodium borohydride addition in mixed solution（More preferable 0.6~1.5 mmol/
L）.Sodium borohydride addition excessively is not easy to form triangular silver nanosheet, and solution colour easily deepens.
Preferably, step（1）In, the molar ratio of the conjugated polyelectrolytes and nano silver is 1:0.5~2.0（More preferably
1:0.6~1.0）.Since nano silver material has conjugated polymer certain quenching effect, when the conjugated polymer of addition with receive
It is better when the ratio of meter Yin >=1.
Preferably, step（1）In, the sum of conjugated polyelectrolytes aqueous solution and Nano silver solution and the volume ratio of buffer solution are
10~40: 100.The volume of buffer solution reaches the validity that matched uniform system total volume half more can guarantee buffer system.
Preferably, step（1）In, the dosage of water be so that the conjugated polyelectrolytes in uniform system a concentration of 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）, the nano silver in uniform system a concentration of 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 so that fluorescent quenching efficiency reduces, nano silver
Concentration is too small, then cannot significantly be etched by over cure acid ion.
It is highly preferred that a concentration of the 0.5 × 10 of the conjugated polyelectrolytes aqueous solution-4~1.5 × 10-4 Mol/L, it is described
A concentration of the 0.5 × 10 of Nano silver solution-4~1.5 × 10-4mol/L。
Preferably, step（1）In, the buffer solution 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 phosphoric acid, boric acid and acetic acid with mass ratio 1:1~3:1~3 mixes.
Preferably, step（1）In, the time being stirred to react is 8~12 min.
Preferably, step（2）In, the time being stirred to react is 20~40 min.
Step（3）In, with（F0-F）/F0As unified reference point, the intensity of fluorescent quenching is represented, the value is bigger, explanation
Quenching is more apparent, 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
Water solubility can improve the sensitivity of detection, 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 the buffer solution of conjugated polyelectrolytes-Nano silver piece, it is made to show
Strong oxidizing property carries out oxide etch to the system, and S is realized by detecting 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 is dexterously combined Nano silver piece with conjugated polyelectrolytes, constitutes new nano composite system, bright
The aobvious sensitivity for improving persulfate detection, simple and practicable, accurate, rapid, highly sensitive, lowest detection is limited to 9 × 10-7
Mol/L, and 1 × 10-6~9 × 10-5Linear good, this method intuitive with fluorescence spectrum performance is detected in the range of mol/L
Selectivity is good, the detection being suitable in the case of more ion interference.
Description of the drawings
Fig. 1 is 3 conjugated polyelectrolytes of embodiment-Nano silver piece system（pH=5）To the selective block diagram of 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 different conjugated polyelectrolytes dosages in conjugated polyelectrolytes-Nano silver piece system to S2O8 2-Fluorescence response figure
（Examples 1 to 5 is the 4th~8 point from left to right；In figure,C P1Indicate conjugated polyelectrolytes in step（1）In the uniform system of gained
Concentration）；
Fig. 5 is different Nano silver piece dosages in conjugated polyelectrolytes-Nano silver piece system to S2O8 2-Fluorescence response figure（Implement
Example 6~9 is the 1st~4 point from left to right；In figure,C AgNPRsIndicate Nano silver piece in step（1）It is dense in the uniform system of gained
Degree）；
Fig. 6 is the differential responses time in conjugated polyelectrolytes-Nano silver piece system to S2O8 2-Fluorescence response figure（Embodiment 10
~14 be the 9th~13 point from left to right）；
Fig. 7 is 3 monodispersed conjugated polyelectrolytes of embodiment-Nano silver piece electron microscope；
Fig. 8 is that S is added in 3 monodispersed conjugated polyelectrolytes of embodiment-Nano silver piece2O8 2-Electron microscope afterwards.
Specific implementation mode
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 chemical structure of general formula is：
, wherein n is 86~110；This is total
Yoke polyelectrolyte is polyfluorene class, and positively charged hair blue-fluorescence contains pyridine groups, has the characteristics that water-soluble.
Conjugated polyelectrolytes reference example 2
Its chemical structure of general formula is：
, wherein n is 160~190；This is total
Yoke polyelectrolyte is polyfluorene class, and positively charged hair blue-fluorescence contains pyridine groups, has the characteristics that water-soluble.
Conjugated polyelectrolytes reference example 3
Its chemical structure of general formula is：
, wherein n is 230~258；This is total
Yoke polyelectrolyte is 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 are added in 0.0900 g 2,7- bis- iodo- 9,9- bis- (6'- bromines hexyl) fluorenes（3.3 g）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 to get white solid product with ether
0.0621 g, 60 % of yield.
The synthetic method of the 2,7- bis- iodo- 9,9- bis- (6'- bromines hexyl) fluorenes 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 is added（0.6 mmol）2,7- diiodo-s 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, is rapidly cooled to room
Temperature is extracted 3 times with dichloromethane, merges organic layer, respectively successively with the aqueous hydrochloric acid solution of 1 mol/L, water and 1 mol/L
NaCl aqueous solutions wash 1 time, then use anhydrous Na2SO4It is dry, filtering, evaporated under reduced pressure, then it will be evaporated product silica gel column chromatography, and
With n-hexane:The volume ratio of chloroform is 9:1 mixed liquor elution, 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-s fluorenes is：By 82.5 mL（86.625 g）CH3COOH、6.6mL（6.6 g）H2O
And 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 precipitation, use the Na of water and 2 mol/L successively 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 (DMSO)
Mixing, under nitrogen protection, stirring are warming up to 150 DEG C, and after 15 min of insulation reaction, solution colour is reddened by yellow, then with speed
1 mL/min is spent, 0.97 mL is instilled（20 mmol, 1 g）Hydrazine hydrate is stood, cooling, and filtering, filter residue washes 5 times with ethyl alcohol, second
Ether washs 3 times,.
Diacetylene pyridine reference example 6
By 0.462 g（0.4 mmol）5 gained tetra-triphenylphosphine palladium of reference example, 0.076 g（0.4 mmol）CuI and 1.90 g（8
mmol）2,6- dibromo pyridines mix, and under nitrogen protection, 25 mL are added（20.989 g）Toluene:The volume ratio of diisopropylamine is
4:2.27 mL are added then with 1 mL/min speed in 1 toluene-diisopropylamine mixed solution（1.578 g）Trimethyl silicon substrate
Acetylene is filtered to remove insoluble matter, then with petroleum ether after reacting 12 h under room temperature:The volume ratio of dichloromethane is 5:1 mixing is molten
Liquid is detached as solvent with silica gel column chromatography, obtains pure intermediate products, then at normal temperatures, and the pure intermediate products of 1.2 g are dissolved in
75 mL（63 g）Tetrahydrofuran:The volume ratio of methanol is 1:14 g K are added in 1 in the mixed solvent2CO3, stir 12 h, mistake
Filter, filtrate concentration, then with petroleum ether:The volume ratio of dichloromethane is 1.5:1 mixed solution uses silica gel column layer as solvent
Analysis separation,.
The synthetic method reference example 7 of conjugated polyelectrolytes reference example 1
1）The mixed solution of 2.5 mL water, 3.75 mL dimethylformamides and 1.3 mL diisopropylamines is led into nitrogen deoxygenation 10
After min, under nitrogen protection, 0.0647 g is added（0.075 mmol）4 gained 2,7- of reference example, bis- iodo- 9,9- bis- (6'- (N,
N, N- trimethyl ammonium)-hexyl) bromine fluorenes, 0.0094 g（0.074 mmol）6 gained 2,6- diacetylenes pyridine of reference example,
0.0087 g（7.5 μmol）5 gained tetra-triphenylphosphine palladium of reference example and 0.0015 g（7.5 μmol）CuI is heated to 50 DEG C,
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）By 1.2 g steps 1）Gained concentrate instills 150 mL stirred with 500 r/min speed with 0.8 mL/min of speed
Acetone-diethyl ether mixed liquor（Acetone:The volume ratio of ether is 75:50,113.724g）In, stand, remove supernatant liquor, lower layer into
Row centrifugal treating, repeats aforementioned operation 2 times, vacuum drying,.
In deionized water by the dissolving of gained conjugated polyelectrolytes, with concentration 1 × 10-4mol/L（It is calculated with repetitive unit）
As storing solution.
The synthetic method reference example 8 of conjugated polyelectrolytes reference example 2
1）The mixed solution of 2.5 mL water, 3.75 mL dimethylformamides and 1.3 mL diisopropylamines is led into 8 min of nitrogen deoxygenation
Afterwards, under nitrogen protection, 0.0647 g is added（0.075 mmol）4 gained 2,7- of reference example, bis- iodo- 9,9- bis- (6'- (N, N,
N- trimethyls ammonium)-hexyl) bromine fluorenes, 0.0095 g（0.075 mmol）6 gained 2,6- diacetylenes pyridine of reference example,
0.0087 g（7.5 μmol）5 gained tetra-triphenylphosphine palladium of reference example and 0.0015 g（7.5 μmol）CuI is heated to 50 DEG C,
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）By 1.8 g steps 1）Gained concentrate instills 200 mL stirred with 400 r/min speed with 0.6 mL/min of speed
Acetone-diethyl ether mixed liquor（Acetone:The volume ratio of ether is 75:50,151.632 g）In, it stands, removes supernatant liquor, lower layer
Centrifugal treating is carried out, repeats aforementioned operation 2 times, vacuum drying,.
In deionized water by the dissolving of gained conjugated polyelectrolytes, with concentration 1 × 10-4mol/L（It is calculated with repetitive unit）
As storing solution.
The synthetic method reference example 9 of conjugated polyelectrolytes reference example 3
1）The mixed solution of 2.5 mL water, 3.75 mL dimethylformamides and 1.3 mL diisopropylamines is led into nitrogen deoxygenation 12
After min, under nitrogen protection, 0.0647 g is added（0.075 mmol）4 gained 2,7- of reference example, bis- iodo- 9,9- bis- (6'- (N,
N, N- trimethyl ammonium)-hexyl) bromine fluorenes, 0.0098 g（0.077 mmol）6 gained 2,6- diacetylenes pyridine of reference example,
0.0087 g（7.5 μmol）5 gained tetra-triphenylphosphine palladium of reference example and 0.0015 g（7.5 μmol）CuI is heated to 50 DEG C,
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）By 2.4 g steps 1）Gained concentrate instills 250 mL third stirred with 700 r/min speed with 1 mL/min of speed
Ketone-ether mixed liquor（Acetone:The volume ratio of ether is 75:50,189.54 g）In, it stands, removes supernatant liquor, lower layer carries out
Centrifugal treating, repeats aforementioned operation 2 times, vacuum drying,.
In deionized water by the dissolving of gained conjugated polyelectrolytes, with concentration 1 × 10-4mol/L（It is calculated with repetitive unit）
As storing 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 lemons are added in 25 mL, the silver nitrate solution of 0.1 mmol/L
Sour three sodium solutions, 1.5 mL, 0.7 mmol/L（K-30, Mw~29000 g/mol）Polyvinylpyrrolidonesolution solution and 60 μ L matter
Measure the hydrogenperoxide steam generator of 30 % of score（Silver nitrate, trisodium citrate, polyvinylpyrrolidone and hydrogen peroxide mass ratio be
1: 31: 72: 160）, after being mixed evenly, disposably rapidly join the hydroboration sodium borohydride of 250 μ L, 100 mmol/L
Change sodium solution, is quickly stirred to react 30 min, which becomes deep yellow by yellow and eventually becomes darkviolet,.
After testing, a concentration of the 1 × 10 of Nano silver piece-4 Mol/L, the nm of the grain size of Nano silver piece≤50, uses ultraviolet spectrometry
Wavelength is in 551 nm after photometer measurement.
The preparation method reference example 11 of buffer solution
It is the mixed acid in 0.04 mol/L（Phosphoric acid, boric acid and acetic acid are with mass ratio 1:1:1 mixes）It is added in aqueous solution
Sodium hydroxide is to pH=5.
A kind of embodiment of the method 1~5 detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver
（1）Respectively by 30 μ L, 40 μ L, 50 μ L, 60 μ L, 70 μ L, 1 × 10-4The water of the conjugated polyelectrolytes reference example 1 of mol/L
Solution and 50 μ L, 1 × 10-410 gained Nano silver piece solution of mol/L reference examples and 500 μ L reference examples, 11 gained buffer solution are dissolved in
In water, water is added to be settled to 1 mL, after being stirred to react 10 min, respectively uniform system 1~5, measure its fluorescence intensity F respectively0；
（2）Respectively in step（1）In the uniform system of gained 1~5, the solution containing over cure acid ion to be measured is added（It is theoretical dense
Degree is 9 × 10-5mol/L）, after being stirred to react 30 min, its fluorescence intensity F is measured respectively；
（3）Calculate separately Y=（F0-F）/F0=0.877,0.898,0.912,0.913,0.912, then by expression over cure acid group from
Formula Y=0.526 × log of relationship between son and fluorescence intensityC(S2O8 2-)+3.044, R=0.955, over cure acid group is obtained respectively
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 3 step of the embodiment of the present invention（1）The uniform system of gained（That is the poly- electrolysis of conjugation
Matter-Nano silver piece system, similarly hereinafter）With different responses, but it is far below to S2O8 2-Influence, illustrate the method for the present invention walk
Suddenly（1）The uniform system of gained is for S2O8 2-There is good selectivity.
As shown in Fig. 2, illustrating 3 step of the embodiment of the present invention（1）The uniform system of gained is to various concentration S2O8 2-Fluorescence tool
There is more apparent response difference.
As shown in figure 3, being 3 step of the embodiment of the present invention（1）The uniform system of gained is to various concentration S2O8 2-Fluorescence response
Linear graph, and in this, as step（3）Calculation formula, calculate contain S2O8 2-The unknown concentration of solution.
As shown in figure 4, being 1~5 step of the embodiment of the present invention（3）Gained Y=（F0-F）/F0Curve graph（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 3 step of the embodiment of the present invention（1）In the uniform system of gained, monodispersed conjugation is poly-
S is added in electrolyte-Nano silver piece2O8 2-S is added in front and back Electronic Speculum graph discovery2O8 2-Afterwards, conjugated polyelectrolytes-Nano silver piece system
By oxide etch, 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, the nm of grain size≤50.
A kind of embodiment of the method 6~9 detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver
（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 examples and 500 μ L reference examples, 11 gained buffer solution are dissolved in water
In, add water 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 step（1）In the uniform system of gained 6~9, the solution containing over cure acid ion to be measured is added（It is theoretical dense
Degree is 8 × 10-5mol/L）, after being stirred to react 30 min, its fluorescence intensity F is measured respectively；
（3）Calculate separately Y=（F0-F）/F0=0.842,0.876,0.856,0.839, then by expression over cure acid ion with it is glimmering
Formula Y=0.526 × log of relationship between luminous intensityC(S2O8 2-)+3.044, R=0.955, it is dense that over cure acid ion is obtained respectively
Degree=6.46 × 10-5, 7.58 × 10-5, 6.92 × 10-5, 6.42 × 10-5 mol/L。
As shown in figure 5, being 6~9 step of the embodiment of the present invention（3）Gained Y=（F0-F）/F0Curve graph（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 embodiment of the method 10~14 detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver
（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 mol/
10 gained Nano silver piece solution of L reference examples and 2500 μ L reference examples, 11 gained buffer solution are soluble in water, add water to be settled to 5 mL, stir
Mix reaction 10 min after, be divided into 5 parts, respectively uniform system 10~14, measure its fluorescence intensity F respectively0；
（2）Respectively in step（1）In the uniform system of gained 10~14, the solution containing over cure acid ion to be measured is added（It is theoretical
A concentration of 6 × 10-5mol/L）, it is stirred to react, 20 min, 25 min, 30 min, 35 min, after 40 min, surveys respectively respectively
Measure its fluorescence intensity F；
（3）Calculate separately Y=（F0-F）/F0=0.772,0.781,0.797,0.803,0.799, then by expression over cure acid group from
Formula Y=0.526 × log of relationship between son and fluorescence intensityC(S2O8 2-)+3.044, R=0.955, over cure acid group is obtained respectively
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, being 10~14 step of the embodiment of the present invention（3）Gained Y=（F0-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 (10)
1. a kind of method detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver, which is characterized in that including following step
Suddenly：
（1）Conjugated polyelectrolytes aqueous solution, Nano silver solution and buffer solution is soluble in water, after being stirred to react, uniform system is obtained,
Measure its fluorescence intensity F0；
（2）In step（1）In the uniform system of gained, the solution containing over cure acid ion to be measured is added, after being stirred to react, measures
Its fluorescence intensity F；
（3）Calculating Y=（F0-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 using conjugated polyelectrolytes-silver detection persulfuric acid ion concentration according to claim 1, feature exist
In：Step（1）In, the conjugated polyelectrolytes are polyfluorene class, and positively charged hair blue-fluorescence contains pyridine groups, has water-soluble
The characteristics of property.
3. the method according to claim 1 or claim 2 for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver, feature
It is：Step（1）In, the chemical structure of general formula of the conjugated polyelectrolytes is：
, wherein during n is 86~258
Integer.
4. the method for using conjugated polyelectrolytes-silver detection persulfuric acid ion concentration according to claim 3, feature exist
In the synthetic method of the conjugated polyelectrolytes includes the following steps：
1）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- diacetylenes 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）By step 1）Gained concentrate instill stirring acetone-diethyl ether mixed liquor in, stand, remove supernatant liquor, lower layer into
Row centrifugal treating repeats aforementioned operation >=1 time, is dried in vacuo,.
5. the method for using conjugated polyelectrolytes-silver detection persulfuric acid ion concentration according to claim 4, feature exist
In：Step 1）In, 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；Step 1）In, 2,7- bis- iodo- 9,9-, bis- (6'- (N, N, N- trimethyl ammonium)-
Hexyl) bromine fluorenes, 2,6- diacetylenes pyridine, tetra-triphenylphosphine palladium and CuI molar ratio be 8~15:8~15: 1:1, it is described
The total mole number of raw material is 0.005~0.030 with the molal volume ratio of water, dimethylformamide and diisopropylamine total volume
mol/L；Step 1）In, the temperature of the heating reaction is 40~60 DEG C, and the time is 12~40 h；Step 2）In, step 1）Institute
Obtain concentrate and step 2）The mass ratio of the acetone-diethyl ether mixed liquor is 0.8~3.0: 100；Step 2）In, the acetone-
The volume ratio of acetone and ether is 1.2~1.8 in ether mixed liquor: 1；Step 2）In, the speed of the instillation is 0.5~1.0
mL/min；Step 2）In, the speed of the stirring is 400~700 r/min.
6. according to one of Claims 1 to 5 method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver,
It is characterized in that：Step（1）In, the nano silver is one or more of Nano silver piece, nano silver wire or Nano silver grain；Institute
State diameter≤50 nm of the grain size of Nano silver piece and Nano silver grain, nano silver wire.
7. the method for using conjugated polyelectrolytes-silver detection persulfuric acid ion concentration according to claim 6, feature exist
In：The preparation method of the Nano silver piece solution is：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 becomes deep yellow by yellow, eventually becomes darkviolet,.
8. the method for using conjugated polyelectrolytes-silver detection persulfuric acid ion concentration according to claim 7, feature exist
In：The silver nitrate, trisodium citrate, polyvinylpyrrolidone and hydrogenperoxide steam generator mass ratio 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
A concentration of 0.5~2.0 mmol/L after sodium hydride addition in mixed solution.
9. according to one of claim 1~8 method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver,
It is characterized in that：Step（1）In, 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 solution is 10~40: 100；The dosage of water is so that the conjugation is poly-
Electrolyte in uniform system a concentration of 2 × 10-6~2 × 10-5 Mol/L, the nano silver are a concentration of in uniform system
2×10-6~2 × 10-5 mol/L；The buffer solution 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 phosphoric acid, boric acid and acetic acid with mass ratio 1:1~3:1~3 mixes.
10. according to one of claim 1~9 method for detecting persulfuric acid ion concentration with conjugated polyelectrolytes-silver,
It is characterized in that：Step（1）In, the time being stirred to react is 8~12 min；Step（2）In, the time being stirred to react
For 20~40 min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660000A (en) * | 2012-04-13 | 2012-09-12 | 湖南师范大学 | Conjugated polyelectrolyte with ratiometric fluorescence signals, preparation method and application thereof |
| CN103360604A (en) * | 2013-07-11 | 2013-10-23 | 华南理工大学 | Conjugated metal polymer photoelectric material with functionalized polarity side-chain radicals and application thereof |
| CN104111246A (en) * | 2014-07-29 | 2014-10-22 | 苏州大学 | Sensing material for trace detection of heavy metal ions as well as preparation method and application of sensing material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660000A (en) * | 2012-04-13 | 2012-09-12 | 湖南师范大学 | Conjugated polyelectrolyte with ratiometric fluorescence signals, preparation method and application thereof |
| CN103360604A (en) * | 2013-07-11 | 2013-10-23 | 华南理工大学 | Conjugated metal polymer photoelectric material with functionalized polarity side-chain radicals and application thereof |
| CN104111246A (en) * | 2014-07-29 | 2014-10-22 | 苏州大学 | Sensing material for trace detection of heavy metal ions as well as preparation method and application of sensing material |
Non-Patent Citations (1)
| Title |
|---|
| YI XIAO ET AL.: "Conjugatedpolyelectrolyte-stabilizedsilvernanoparticlescoupled with pyrenederivativeforultrasensitive fluorescentdetection of iodide", 《TALANTA》 * |
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|---|---|---|---|---|
| CN110563636A (en) * | 2019-09-11 | 2019-12-13 | 湖南师范大学 | conjugated polymer containing pyrene-pyridine group and synthetic method and application thereof |
| CN110563636B (en) * | 2019-09-11 | 2020-12-08 | 湖南师范大学 | Conjugated polymer containing pyrene-pyridine group and synthetic method and application thereof |
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