CN104817461A - Method for preparing conjugated microporous polymers (CMPs) from dendritic material through electro-polymerization and application of CMPs in fluorescence sensing - Google Patents
Method for preparing conjugated microporous polymers (CMPs) from dendritic material through electro-polymerization and application of CMPs in fluorescence sensing Download PDFInfo
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Abstract
The invention relates to preparation of a CMPs film from an electro-polymerizable dendritic material and application of the CMPs in fluorescence sensing, belonging to the technical field of fluorescence sensing. The CMPs film prepared from the electro-polymerizable dendritic material through electro-polymerization can be applied to fluorescence sensing, and in particular, is applicable as a fluorescent probe to detection of TNT gas, Fe<3+> ions and benzene gas. The dendritic material is composed of cores A, branches B and electroactive units C. The cores A may be pyrene, tetraphenyl silicon, tetraphenyl ethylene, spirofluorene, etc.; the branches B comprise phenylene group, and each core A is connected with m branches B (wherein m is 1, 2, 3 or 4); and the electroactive units C may be furan, pyrrole, thiophene, carbazole, diphenylamine or triphenylamine, and the number of the electroactive units C is determined by the structural properties of the branches B. The method for preparing the CMPs from the dendritic material is simple, and the CMPs have the characteristics of high sensitivity, good repeatability and good practicality when applied in fluorescence sensing.
Description
Technical field
Dendrimer materials electropolymerization prepares conjugation microporous polymer (CMPs) film and such application of conjugation microporous polymer (CMPs) film in fluorescence sense, belong to fluorescence sense technical field, being specifically related to a class can the dendrimer materials of electropolymerization, the CMPs film prepared by electrochemical polymerization by it, and this CMPs film application in fluorescence sense, especially may be used for detecting TNT gas, Fe as fluorescent probe
3+ion and benzene gas.
Background technology
Conjugation microporous polymer (CMPs) is the organic microporous polymer of a class (MOPs), by the polymkeric substance that kinetic control is formed, what present is a kind of unformed state, has the characteristics such as larger specific surface area, high chemical stability and thermostability.CMPs not only correct for the misperception that it is believed that and cannot regulate and control the aperture of amorphous microporous material, and CMPs material has the advantage of the aspects such as adjustment aperture, CMPs material is become most possible " the organic molecule sieve " that replace traditional inorganic porous material, thus causes the great interest of scientists.
The synthesis of CMPs and application belong to a new research field, from 2007, since people's reported first such as professor Cooper of Liverpool, UK university, have had the CMPs material of a lot of new texture to be seen in report.More representational material is polyphenylacetylene (PAE) compounds, polyphenylene ethylene (PPV), amino benzenes compounds and triazine framework material (CTF) etc.Although the approach of synthesis CMPs material is a lot, but usually need to adopt expensive transition metal as catalyzer or monomer in the synthetic method of current existing CMPs, and after reaction, be difficult to realize being separated completely of catalyzer and CMPs, because which limit the application of CMPs, and the solubleness of this kind of material is relatively low, and processing characteristics is poor, be mostly to exist with pulverulence, its film is difficult to obtain, and limits the further application of this kind of material.Although certain methods can be used to preparation CMPs film, such as spatial induction growth method, layer by layer crosslinking, teeming practice etc., but all there are some problems, as shortcomings such as preparation method is complicated, thin film stability is poor, the permeability (hole of film) of film differences, the preparation method therefore developing new CMPs material and CMPs film is the challenge that researcher faces.
But by CMPs film prepared by electrochemical oxidation method, because film thickness is controlled, morphology controllable, go ionogen to adulterate the advantage such as controlled, the interwoven mesh film formed, ensure that the permeability of its film in turn ensure that the high fluorescent of film on the one hand; Again because electropolymerization film is dissolved in any organic solvent hardly, the stability of its film enhances its applicability.
CMPs film has high conjugacy and porous feature, therefore has certain application potential at photoelectricity and sensory field.Such as detect TNT gas, Fe
3+ion, benzene gas etc.As everyone knows, 2，4，6-trinitrotoluene (TNT) is mainly used in military affairs and industry, but the environmental pollution that causes of TNT and public safety hidden danger bring huge harm to the mankind, and therefore TNT detects the great attention obtaining people; Fe
3+ion is as the essentially consist element of life entity, significant in many bioprocesss; Benzene gas is owing to having the carinogenicity of height, and in daily finishing, indoor often occur the phenomenons such as benzene exceeds standard.Therefore the fluorescent probe of these three kinds of materials is significant.
Summary of the invention
The object of the present invention is to provide a class can the dendrimer materials of electropolymerization, this material can be prepared into CMPs film by electropolymerization method, and CMPs film is detected TNT gas, Fe as fluorescent probe
3+ion and benzene gas.Such material preparation method is simple, highly sensitive, reproducible, practical.
1, can the dendrimer materials of electropolymerization, be the Organic Electricity polymeric material containing electroactive group, its structural formula is as follows:
Such dendrimer materials is made up of core A, branch B and electroactive unit C.Through optimizing, we select the material containing biphenyl structural (each phenyl ring is connected by carbon-carbon single bond) to construct molecular backbone chain skeleton.Core A can be pyrene, tetraphenyl-silicon, tetraphenyl ethylene, spiral shell fluorenes etc.; Branch B is made up of phenylene, and each core A connects m branch B (m is 1,2,3 or 4); Electroactive unit C can be furans, pyrroles, thiophene, carbazole, pentanoic or triphenylamine, and the number of electroactive unit C is determined by the textural property of branch B.In further preferably, implement angle from concrete, we select, and core A be pyrene, branch B be phenylene as molecular backbone chain skeleton, common and stable triphenylamine is as electroactive unit C.
The structural formula of core A compound is as follows:
The structural formula of branch B compound is as follows:
The structural formula of electroactive unit C compound is as follows:
By optimal screening further, we have synthesized compound P1-G1 and P1-G2, its structural formula as shown in Equation 1:
Core A: the centronucleus determining character, for the precondition of film fluorescence sensing
In the design of dendroid luminescent material, centronucleus determines the glow color of material and the geometric configuration of molecule usually.Pyrene has excellent photoluminescent property, as long fluorescence lifetime, pure blue fluorescence, high carrier mobility.These make it meet basic demand as building organic photoelectrical material structural unit.Although under strong solution or solid conditions, it very easily forms π-π gathering/excimer, fluorescent quenching and luminous quantum efficiency is caused to reduce, but effectively can reduce its π-π by molecular designing to assemble, thus the luminous efficiency keeping it higher, thus provide premise for it is applied to film fluorescence sensing.
Branch B: rigid element, the comparatively large and porous cave in branch of volume; Add porousness and the stability of material
For dendrimer, the adjustment of " branch " is relatively flexible, can regulate performance and the function of compound by introducing different branches and different algebraically.Phenylene class (phenylene) dendrimer has the retainable chemical structure of strong rigid shape, good stability, is easy to the characteristics such as functionalization.Using " branch " of polyphenylene quasi-molecule as dendrimer, not only can increase the rigidity of dendrimer, increase its porousness, and under the porous performance under its solution state can being remained to state of aggregation.
In addition, the volume of " branch " also can affect the hole size after film forming, the large generation of volume of " branch " sterically hindered is conducive in dendrimer, the constructing of intermolecular hole, and the packing of molecules that can effectively reduce under filminess, thus under the porous performance under solution state is remained to state of aggregation.
Terminating functional groups C: the peripheral molecule with electrochemical activity, electropolymerization prepares CMPs film
Triphenylamine (TPA) molecule is a kind of unit of high electrochemical activity, there is lower oxidizing potential, the polymeric film of highly cross-linked network structure can be prepared by electrochemical polymerization method, reaction conditions is gentle, do not need catalyzer, the film morphology of film morphology, the regulation and control of function can be realized by the change of electrochemical parameter, and product is nearly all the dimer of triphenylamine within the scope of certain potentials, structure is clear and definite, and its mechanism is mainly divided into two steps: in (a) solution, first aniline monomer forms the ammonium cation of aniline salt with protonic acid; B () this positively charged ion is oxidized to radical cation again, it is polymerized with the ammonium cation of the aniline salt in solution dimer (TPB) (as shown in Equation 2) that form aniline.
Each dendrimer contains the crosslinked film that multiple triphenylamine molecule is conducive to effectively being formed conjugation, strengthen its conjugated degree, and the increase being formed with the permeability (hole) being beneficial to film of cross-linked network, and crosslinking structure secures molecular position, the porous pattern under molecule liquid state is conducive to remain to filminess, and film not easily undergoes phase transition, excellent in stability.
2, the preparation of CMPs film
The selection of 2.1 preparation conditions
Electrochemistry is prepared CMPs film and is completed in three-electrode system, primarily of working electrode, reference electrode and form electrode.The working electrode used is redox noble electrode, and it stably can work, such as, with the translucent optical electrode that tin indium oxide (ITO) is representative in mensuration potential areas; Supporting electrode Main Function is the loop forming a conducting with working electrode, has redox inertia and the electrode do not reacted with solution medium all can be used as supporting electrode, such as gold, platinum, lead, titanium and Graphite Electrodes; Reference electrode used in the present invention can be " silver-silver ion electrode ", " silver-silver chloride electrode " or " saturated calomel electrode ", thus determines working electrode potential (Ma, H.; Yao, L.; Li, P.; Ablikim, O.; Cheng, Y.; Zhang, M.Chemistry-A EuropeanJournal, 2014,20,11655), all can buy with the form of commodity with upper electrode material and obtain.Electrolyte solution is added in three-electrode system, electrolyte solution is made up of electroanalysis solvent methylene dichloride and supporting electrolyte tetrabutylammonium perchlorate, add in electrolyte solution of the present invention can the dendrimer materials of electropolymerization, the electrochemical method adopted is cyclic voltammetry, thus prepares CMPs film on the working electrode (s.
The aftertreatment of 2.2CMPs film
When working electrode takes out from electrolytic solution, because the compound not carrying out electrochemical reaction in solution is attached to CMPs film, so will clean CMPs film.Be the one in the N,N-dimethylacetamide of 80% ~ 99%, acetonitrile, toluene, methylene dichloride, hexanaphthene, pyridine, benzyl cyanide for clean the solution of CMPs film can be purity, or the mixing of above-mentioned solvent, scavenging period is 20s ~ 10min.
2.3 after preferably CMPs membrane-film preparation process as follows:
In electrolyte solution, the concentration of P1-G2 is 2 × 10
-5~ 8 × 10
-5mol/L, supporting electrolyte is tetrabutylammonium perchlorate (TBAP), and concentration is 0.05 ~ 0.3mol/L, electroanalysis solvent dichloromethane solution; Working electrode is ITO electrode, and area is 1cm
2~ 2cm
2; Supporting electrode is titanium plate, and area is 4cm
2; Reference electrode is silver-silver ion electrode; The electrochemical apparatus used is Shanghai Chen Hua company CHI660C electrochemical workstation, cyclic voltammetric optimum configurations encloses for scanning the number of turns 8, voltage is applied between working electrode and supporting electrode, take-off potential is-0.2V to 1.1V, sweep velocity is 100mV/s, thus in ITO electrode, prepare CMPs film, then adopt dichloromethane solvent to clean CMPs film as eluent.
Accompanying drawing explanation
The mass spectrum of Fig. 1: P1-G2;
The electropolymerization multi-turn cyclic voltammetry curve of Fig. 2 a:P1-G2; Take tetrabutylammonium perchlorate as ionogen, P1-G2 concentration is 1 × 10
-5mol/L, cyclic voltammetry scan interval is-0.2V ~ 1.1V.Arranging sweep velocity is 100mV/s, and the scanning number of turns is 8 circles.Illustration in Fig. 2 a is that P1-G2CMPs after polymerization is without support transparent film photo;
Fig. 2 b:I figure is the three-dimensional plot of P1-G2CMPs film surface appearance (AFM), and II figure is the orthographic plan of AFM; III figure and IV figure are respectively the local of P1-G2CMPs film and overall transmission electron microscope picture (TEM), more than can prove that electropolymerization method can prepare P1-G2CMPs film;
Fig. 3 a:P1-G2CMPs film is exposed to TNT gas 0s, 20s, 60s, 120s, and fluorescence intensity is curve over time; Illustration is the contrast figure that film is exposed to fluorescence intensity change before and after TNT gas: before film is exposed to TNT gas, film sends blue light, after being exposed to TNT gas, and fluorescent quenching;
Fig. 3 b:P1-G2CMPs film is exposed to TNT (2,4,6-trotyl), DNT (2,4-dinitrotoluene (DNT)), RDX (ring cyclonite three ammonium nitrate), Tetryl (tetryl), HMX (cyclotetramethylene-tetranitramine), cancellation rate curve (cancellation rate deducts the intensity after cancellation by initial strength to calculate divided by initial strength again) in PETN (trinitrol) gas; Illustration is film cycle detection curve: repeatedly loop test, proves that P1-G2CMPs film has repeatability.
Fig. 4 a:P1-G2CMPs film is exposed to A1
3+(trivalent aluminium), Co
2+(divalence cobalt), Ni
2+(nickelous), Cr
3+(trivalent chromium), Pb
2+(divalence is plumbous), Zn
2+(divalent zinc), Cu
2+(cupric), Fe
3+(ferric iron) and Hg
2+fluorescent quenching rate curve in (bivalent mercury); Illustration is that P1-G2CMPs is exposed to Fe
3+(this curve is according to Fe in titration matched curve in solion
3+ionic concn is 1 × 10
-6~ 1 × 10
-5fluorescence intensity change in scope is calculated);
Fig. 4 b:P1-G2CMPs film hybrid ionic interference under to Fe
3+ion (1 × 10
-4) detection curve (be respectively: initial strength curve, add mixing interfering ion (Co
2+, Ni
2+, Zn
2+, Cu
2+) after curve, then add Fe
3+curve after ion); Illustration is film cycle detection curve: repeatedly loop test, proves that P1-G2CMPs thin film is repeatable.
Fig. 5 a:P1-G2CMPs film is exposed to the Fluorescence Increasing rate curve in benzene gas, toluene gas, chlorobenzene gas; Illustration is the contrast figure that film is exposed to fluorescence intensity change before and after benzene gas: before film is exposed to benzene gas, film sends blue light, after being exposed to benzene gas, and Fluorescence Increasing.
Fig. 5 b:P1-G2CMPs film is exposed to benzene gas 0s, 20s, 60s, 120s, and fluorescence intensity strengthens curve over time; Illustration is film cycle detection curve: repeatedly loop test, proves that P1-G2CMPs film has repeatability.
Embodiment
Embodiment 1: the synthesis of compound P1-G2:
The synthesis of P1-G2
Compound 4 and compound 5 derive from the general institute of German horse.Compound 4 (80.0mg, 0.042mmol) and compound 5 (450.2mg, 0.626mmol) are dissolved in 15mL o-Xylol.Then heat 2 days at 160 DEG C.The product with methylalcohol obtained after reaction is precipitated out, and filters.Through silicagel column, eluent is methylene dichloride and normal hexane (volume ratio is 6:4).End product is by gel permeation chromatographic column purifying, and solvent is toluene.Finally obtain 150mg yellow solid, i.e. P1-G2, productive rate is 50%.
1h NMR (700MHz, CD
2cl
2, 300K) and δ 7.81-7.65 (m, 6H), 7.48-7.36 (m, 12H), 7.23-6.28 (m, 376H).
13c NMR (176MHz, CD
2cl
2, 298K) and δ 148.04,145.64,145.29,142.08,141.99,140.94,140.89,140.68,140.61,140.44,139.54,139.45,139.34,139.28,139.14,138.72,138.55,138.31,136.88,136.15,135.51,132.82,132.01,131.41,131.15,130.31,129.33,129.26,128.94,128.62,128.31,128.24,128.20,127.97,127.80,127.11,126.54,125.91,125.80,123.88,123.66,123.50,122.57,122.42. mass spectrum: C
568h
394n
16theoretical value: 7443.1, actual value: 7440.8 [M-2H]
+. (as Fig. 1)
The preparation of embodiment 2:P1-G2CMPs film
In electrolyte solution, the concentration of P1-G2 is 10
-5mol/L, supporting electrolyte is tetrabutylammonium perchlorate (TBAP), and concentration is 0.1mol/L, and electroanalysis solvent is methylene dichloride; Working electrode is ITO electrode, and area is 1.5cm
2; Supporting electrode is titanium plate, and area is 4cm
2; Reference electrode is silver-silver ion electrode; The electrochemical apparatus used is Shanghai Chen Hua company CHI660C electrochemical workstation, and cyclic voltammetric optimum configurations encloses for scanning the number of turns 8, and take-off potential is-0.2V to 1.1V, and sweep velocity is 100mV/s.We adopt dichloromethane solvent as the cleaning of eluent to P1-G2CMPs film.Through weak acid treatment (10
-5mol/L), can obtain without supporting transparent film (about 50nm) (as Fig. 2).
Embodiment 3:P1-G2CMPs thin film testing TNT gas
TNT powder will be put in cuvette, powder covers bottom cuvette, then on TNT, filter paper is covered, cover lid above cuvette, place after 60 minutes, put into the P1-G2CMPs film that embodiment 2 prepares fast, fluorescence spectrophotometer in time 0s, 20s, 60s, 120s records fluorescence intensity.Be exposed in TNT after 20s, P1-G2CMPs film fluorescence intensity cancellation 62.56%, is exposed in TNT after 120s, fluorescence intensity cancellation 82.05%.
P1-G2CMPs film has also carried out the test (DNT, RDX, Tetryl, HMX, PETN) of multiple explosive substance, finds that P1-G2CMPs film only has specificly-response to TNT.P1-G2CMPs film after being exposed to TNT gas is placed in methanol solution, stirs 60 minutes, be then placed in vacuum drying oven 45 DEG C of dryings 3 hours of nitrogen protection.Again film is placed in TNT gas, tests.Although repeat 5 times, fluorescence intensity still cancellation 70% (as Fig. 3) after 120s.
To sum up show due to P1-G2CMPs film have that characteristic is strong to TNT, the time of response short with the advantage such as can to reuse, so P1-G2CMPs film is applicable to TNT gas sensing.
Embodiment 4:P1-G2CMPs thin film testing Fe
3+ion
The kind of the ion detection of P1-G2CMPs film has A1
3+, Co
2+, Ni
2+, Cr
3+, Pb
2+, Zn
2+, Cu
2+, Fe
3+and Hg
2+be Cl
-salt.First measure the fluorescence intensity of P1-G2CMPs film itself, then add different concns (1 × 10 respectively
-6~ 1 × 10
-4m) metal ion solution, surveys the fluorescence intensity of fluorescence sense film again after stirring.When adding 1 × 10
-4m Fe
3+ion, fluorescence intensity cancellation 89%.
Will be exposed to Fe
3+cMPs film after ion is placed in EDTA solution, rinses 3 times, then uses washed with methanol 3 times.Then vacuum drying oven 45 DEG C of dryings 3 hours of nitrogen protection are placed in.And then film is placed in Fe
3+in solion, test.Although repeat 5 times, fluorescence intensity is cancellation 72% still.(as Fig. 4)
To sum up show because P1-G2CMPs film is to Fe
3+ion have characteristic strong, highly sensitive with the advantage such as can to reuse, so P1-G2CMPs film is applicable to Fe
3+ion sensor.
Embodiment 5:P1-G2CMPs thin film testing benzene gas
P1-G2CMPs film is tested benzene gas, toluene gas, chlorobenzene gas respectively, and fluorescence spectrophotometer is 0s in time, and 20s, 60s, 120s record fluorescence intensity.Only have the response speed of benzene gas the fastest, be exposed in benzene after 20s, P1-G2CMPs film fluorescence intensity enhancing 200%, be exposed in benzene gas after 120s, fluorescence intensity strengthens 400%.
To be exposed to the CMPs film after benzene gas and be placed in vacuum drying oven 45 DEG C of dryings 3 hours of nitrogen protection, and then film will be placed in benzene gas, again test.Although repeat 5 times, after 20s, fluorescence intensity still strengthens about 200% (as Fig. 5).
To sum up show due to P1-G2CMPs film have that characteristic is strong to benzene gas, the time of response short with the advantage such as can to reuse, so P1-G2CMPs film is applicable to benzene gas sensing.
Claims (9)
1. can the dendrimer materials of electropolymerization, it is made up of core A, branch B and electroactive unit C, and its structural formula is as follows:
M is 1,2,3 or 4, and the number of electroactive unit C is determined by the textural property of branch B;
The structural formula of core A compound is as follows,
The structural formula of branch B compound is as follows,
The structural formula of electroactive unit C compound is as follows,
2. as claimed in claim 1 can the dendrimer materials of electropolymerization, it is characterized in that: its structural formula is as follows,
3. a conjugation microporous polymer film, is characterized in that: prepared by electrochemical polymerization by the compound described in claim 1 or 2.
4. conjugation microporous polymer film as claimed in claim 3, is characterized in that: described electrochemical polymerization is cyclic voltammetry.
5. conjugation microporous polymer film as claimed in claim 4, is characterized in that: it is completing by working electrode, reference electrode and the three-electrode system that forms electrode that cyclic voltammetry prepares conjugation microporous polymer film; Namely in above-mentioned three-electrode system, electrolyte solution is added, add in electrolyte solution again described in claim 1 or 2 can the dendrimer materials of electropolymerization, between working electrode and supporting electrode, apply voltage, thus prepare its conjugation microporous polymer film on the working electrode (s.
6. conjugation microporous polymer film as claimed in claim 5, is characterized in that: working electrode is translucent optical electrode; Supporting electrode is gold, platinum, lead, titanium or Graphite Electrodes; Reference electrode is " silver-silver ion electrode ", " silver-silver chloride electrode " or " saturated calomel electrode ".
7. as claimed in claim 6 can the application of dendrimer materials in fluorescence sense of electropolymerization, it is characterized in that: can the concentration of dendroid material of electropolymerization be 2 × 10 in electrolyte solution
-5~ 8 × 10
-5mol/L; Supporting electrolyte is tetrabutylammonium perchlorate, and concentration is 0.05 ~ 0.3mol/L; Electroanalysis solvent dichloromethane solution; Working electrode is ITO electrode, and area is 1cm
2~ 2cm
2; Supporting electrode is titanium plate, and area is 4cm
2; Reference electrode is silver-silver ion electrode.
8. the conjugation microporous polymer film application fluorescence sense in of claim 3-7 described in any one.
9. the application of conjugation microporous polymer film in fluorescence sense as claimed in claim 8, is characterized in that: be for detecting TNT gas, Fe as fluorescent probe
3+ion or benzene gas.
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| CN109988097A (en) * | 2019-01-28 | 2019-07-09 | 吉林大学 | A kind of dendrimer organic fluorescence materials and its application and a kind of fluorescence membrane and preparation method thereof |
| CN110229311A (en) * | 2019-06-17 | 2019-09-13 | 辽宁大学 | Porous organic polymer LNUs of one kind structural unit containing pyrene and its preparation method and application |
| KR20190138424A (en) * | 2018-06-05 | 2019-12-13 | 울산과학기술원 | Conjugated microporous polymers film and manufacturing method the same |
| CN112033889A (en) * | 2020-09-30 | 2020-12-04 | 北方工业大学 | Method for detecting medium salt corrosion resistance of laser cladding coating |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106898492A (en) * | 2017-01-16 | 2017-06-27 | 华南师范大学 | A kind of preparation method and applications for being conjugated microporous polymer film |
| CN106898492B (en) * | 2017-01-16 | 2018-07-06 | 华南师范大学 | A kind of preparation method and applications for being conjugated microporous polymer film |
| KR20190138424A (en) * | 2018-06-05 | 2019-12-13 | 울산과학기술원 | Conjugated microporous polymers film and manufacturing method the same |
| KR102127439B1 (en) | 2018-06-05 | 2020-06-26 | 울산과학기술원 | Conjugated microporous polymers film and manufacturing method the same |
| CN109988097A (en) * | 2019-01-28 | 2019-07-09 | 吉林大学 | A kind of dendrimer organic fluorescence materials and its application and a kind of fluorescence membrane and preparation method thereof |
| CN110229311A (en) * | 2019-06-17 | 2019-09-13 | 辽宁大学 | Porous organic polymer LNUs of one kind structural unit containing pyrene and its preparation method and application |
| CN110229311B (en) * | 2019-06-17 | 2022-03-25 | 辽宁大学 | Porous organic polymers LNUs containing pyrene structural units and preparation method and application thereof |
| CN112033889A (en) * | 2020-09-30 | 2020-12-04 | 北方工业大学 | Method for detecting medium salt corrosion resistance of laser cladding coating |
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