CN107286327B - It is a kind of for quickly detecting the fluorescent test paper and preparation method thereof of explosive, quickly detect explosive method - Google Patents
It is a kind of for quickly detecting the fluorescent test paper and preparation method thereof of explosive, quickly detect explosive method Download PDFInfo
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Abstract
The present invention relates to a kind of for quickly detecting the fluorescent test paper and preparation method thereof of explosive, quickly detects the method for explosive.The fluorescent test paper includes test paper ontology, and load has graphene composite material on the test paper ontology, and the graphene composite material includes polymer shown in graphene and Formulas I, and polymer shown in Formulas I is grapheme modified in the form of non-covalent bond.Fluorescent test paper for quickly detection explosive of the invention, is green fluorescence under 365nm ultraviolet light, and after contacting the liquid containing explosive, fluorescence intensity reduces the quick naked eyes detection, it can be achieved that explosive containing nitro (especially picric acid)；Method using fluorescent test paper detection explosive is easy to operate, at low cost, realizes the fast qualitative detection to explosive.
Description
Technical field
The invention belongs to explosives detection techniques fields, and in particular to a kind of for quickly detecting the fluorescent test paper of explosive
And preparation method thereof, while also disclosing a kind of method that explosive is quickly detected using the fluorescent test paper.
Background technique
Picric acid (2,4,6- trinitrophenols, PA) is a kind of important nitro-aromatic compound, be widely used in leather,
The fields such as pharmacy, fuel.However, picric acid is also a kind of common explosive and highly toxic environmental contaminants, to skin, eye
The toxic effect of eyeball, respiratory tract, Long Term Contact can also damage liver and kidney.With the fast development of China's industry,
The picric acid being discharged into environment increases with the increase of discharged volume of industrial waste water, causes environmental pollution and ecological disruption.Cause
This, highly sensitive detection picric to trace in water body has important realistic meaning.
Currently, picric detection mostly uses gas chromatography and high performance liquid chromatography, although picric acid may be implemented
Highly sensitive detection, but need to carry out sample pre-treatment, it is complicated for operation and take a long time, is at high cost, cannot be quickly real
When detection water body in picric content.In contrast, fluorescence analysis has fast response time, high sensitivity, easy to operate
The advantages that, it is very popular in recent years.Most fluorescent optical sensor is turned using the Photoinduced Electron between fluorescent molecule and picric acid
It moves, the fluorescence of fluorescent molecule is quenched this principle and realizes, such as N- n-hexyl -4- [2- (3- phenylthiourea)-ethylamino] -
1,8- naphthalimide (HTN) (shine journal, 2015,36,39-44), polycyclopentadiene silicane doping chitosan fluorescence sense are thin
Film (CN101864097B), allyl tetraiodofluorescein (CN102830098A), three (benzimidazole) benzene-like compounds
(CN103739555B), two (benzimidazole) naphthalene compounds (CN106008358A) etc..
2001, the Tang Benzhong academician of Hong Kong University of Science and Thchnology had found with aggregation-induced emission (Aggregation-
Induced emission, AIE) effect compound, this kind of compound is in solution state since Internal Rotations of Molecules causes to excite
State energy is decayed with unirradiated form, generates weak fluorescent emission；Blocked rotation when state of aggregation, it is suppressed that non-radiative energy turns
It changes, discharges excited energy with forms of radiation and generate fluorescence.AIE molecule is imaged in vivo, biological monitoring, photoelectric material
Etc. have wide application.In recent years, the compound with AIE effect is also commonly used for picric detection
(Polymer,2012,53,3163-3171；Macromol.Rapid Commun.,2012,33,164-171；
J.Mater.Chem.,2011,21,4056-4059；Polym.Chem.,2012,3,1481-1489；Macromolecules,
2010,43,4921-4936).But the material with AIE effect is fabricated to fluorescent test paper strip, for the quick of explosive
Detection has not been reported.
Summary of the invention
The object of the present invention is to provide a kind of for quickly detecting the fluorescent test paper of explosive.
A second object of the present invention is to provide a kind of for quickly detecting the preparation method of the fluorescent test paper of explosive.
Third object of the present invention is to provide a kind of methods of quick detection explosive using above-mentioned fluorescent test paper.
In order to achieve the goal above, the technical scheme adopted by the invention is that:
It is a kind of for quickly detecting the fluorescent test paper of explosive, including test paper ontology, load has stone on the test paper ontology
Black alkene composite material, the graphene composite material include polymer shown in graphene and Formulas I, polymer shown in Formulas I with
Non-covalent bond form is grapheme modified；
In Formulas I, n is 8~20；R1、R2It is independently selected from C1~C6Alkyl, C1~C6Alkoxy or hydrogen.Wherein,
The alkyl can be straight chained alkyl or the alkyl with branch；The alkoxy can be unbranched alkoxy or the alcoxyl with branch
Base.
Preferably, in Formulas I, R1、R2It is independently selected from methyl, ethyl, butyl, hexyl, methoxyl group, ethyoxyl, fourth oxygen
Base, hexyloxy or hydrogen.
Polymer shown in Formulas I is the polymer with aggregation-induced emission effect, be a kind of functional group containing tetraphenyl ethylene,
The AIE polymer of structure novel；By the in-situ reducing of graphene oxide, in the presence of the polymer, realize to graphene
Non-covalent bond modification, be prepared for dissolving in the graphene composite material of organic solvent, the composite material have apparent AIE effect
It answers, and AIE effect is higher than polymer itself.
The synthesis of polymer shown in Formulas I with aggregation-induced emission effect uses Suzuki method.
The preparation method of the above-mentioned polymer with aggregation-induced emission effect, including the following steps:
1) in zinc powder, TiCl4Under the conditions of existing, 4,4 '-dibromobenzo-phenones are dissolved in solvent with compound 1 and are carried out
Compound 2 is made in back flow reaction, separating-purifying；Compound 1, the structural formula of compound 2 are as follows:
2) under the conditions of existing for alkaline matter, the palladium catalyst, compound 2, connection boric acid pinacol ester are added in solvent
It is reacted, separating-purifying obtains compound 3；The structural formula of compound 3 is as follows:
3) under the conditions of existing for alkaline matter, the palladium catalyst, by 3,6- dibromo carbazole, compound 3 be added in solvent into
Row reaction, separating-purifying obtain polymer shown in Formulas I.
In step 1), the reaction carries out under protective atmosphere, and the protective atmosphere is nitrogen or argon gas；Solvent used
For tetrahydrofuran (THF).Preferably, the zinc powder after taking activation is added in THF, and TiCl is added dropwise under ice bath4, heated after being added dropwise
Flow back 2h, obtains mixture A；4,4 '-dibromobenzo-phenones and 4- butoxy benzophenone are first dissolved in THF, solution is made, then
Acquired solution is added in mixture A, back flow reaction is overnight.Wherein, 4,4 '-dibromobenzo-phenones and 4- butoxy benzophenone
Molar ratio be 1:1；4,4 '-dibromobenzo-phenones and zinc powder, TiCl4Molar ratio be 1:6~9:3~6.
The concrete operations of the step 1) separating-purifying are as follows: system is cooled to room temperature after reaction, it is molten with potassium carbonate
Liquid quenching reaction, filtering, washs filter cake for several times with methylene chloride, filtrate merges organic phase after methylene chloride extracts, and is spin-dried for molten
Agent, with chloroform/petroleum ether (1/20, v/v) for eluent, after silica gel column chromatography separating-purifying, it is dry to get.
In step 2), alkaline matter used is potassium acetate；Palladium catalyst used is (1,1'- bis- (diphenylphosphinos)
Ferrocene) palladium chloride.
In step 2), solvent used is Isosorbide-5-Nitrae-dioxane；The reaction carries out under protection of argon gas, and reaction temperature is
75~85 DEG C.Preferably, it is stirred overnight and is reacted at 80 DEG C.Wherein, the molar ratio of compound 2 and connection boric acid pinacol ester
For 1:2~3；The molar ratio of compound 2 and alkaline matter is 1:6；The dosage of palladium catalyst (is rubbed for the 2%~5% of compound 2
That percentage).
The concrete operations of the step 2) separating-purifying are as follows: end of reaction pours into system in distilled water, uses ethyl acetate
Extraction repeatedly, merges organic phase, and after anhydrous magnesium sulfate is dry, filtering is elution with ethyl acetate/n-hexane (1/15, v/v)
Agent, after silica gel column chromatography separating-purifying, it is dry to get.
In step 3), alkaline matter used is potassium carbonate；Palladium catalyst used is tetrakis triphenylphosphine palladium.
In step 3), the reaction carries out under protective atmosphere, and the protective atmosphere is nitrogen or argon gas；Solvent used
For the mixed solvent of water and tetrahydrofuran；Preferably, the volume ratio of water and tetrahydrofuran is 1:3.The temperature of the reaction is 60
DEG C, the time is 2~5 days.Wherein, 3,6- dibromo carbazole, compound 3, alkaline matter molar ratio be 1:1:10；Palladium catalyst
Dosage is 3%~5% (molar percentage) of 3,6- dibromo carbazole.
The concrete operations of the step 3) separating-purifying are as follows: after reaction, reaction solution is cooled to room temperature, is directly added into first
Solid is precipitated by methanol is added after reaction solution reduced pressure removing THF in alcohol, and solid is collected after filtering；The a small amount of THF of filter cake
After dissolution, being added drop-wise in methanol is precipitated solid, crosses filter solid, repeats above-mentioned methanol reprecipitation operation three times；By consolidating for collection
Soma it is dry to get.
The graphene composite material is under the polymer existence condition shown in Formulas I, also by the original position of graphene oxide
Made of original, polymer shown in Formulas I and the mass ratio for forming the graphene oxide of graphene are 5~10:1.
The graphene composite material is prepared by method comprising the following steps:
A) polymer solution is made in polymer shown in Formulas I；
B) graphene oxide dispersion is mixed with polymer solution, hydrazine hydrate back flow reaction is added, passes through after reaction
Ultrasound, centrifuge separation take supernatant to remove solvent, be drying to obtain.
In step a), preparing solvent used in polymer solution is tetrahydrofuran (THF)；Preferably, every 1mg polymer pair
Solvent 0.2mL should be used.
In step b), in the graphene oxide dispersion, solvent is tetrahydrofuran, and every 1mg graphene oxide correspondence makes
With 1~10mL of solvent.When preparing graphene oxide dispersion, graphene oxide (GO) is added in tetrahydrofuran, ultrasound 20
~60min makes it be uniformly dispersed.
In step b), when graphene oxide dispersion is mixed with polymer solution, the matter of polymer and graphene oxide
Amount is than being 5~10:1.When the two mixes, graphene oxide dispersion is added drop-wise in polymer solution, after stirring 2h, is added
Hydrazine hydrate.
The dosage of the hydrazine hydrate are as follows: every 1mg graphene oxide is corresponding to use 0.020~0.030mL of hydrazine hydrate.Water is added
After closing hydrazine, time of back flow reaction is 8~for 24 hours.After reaction, system is cooled to room temperature carries out ultrasound again.Preferably, ultrasonic
Time be 20~40min.
The revolving speed of the centrifuge separation is 8000~11000rpm, and the time is 10~30min.Centrifuge separation gained supernatant
After solvent is removed under reduced pressure, obtained solid is dried overnight to get the graphene composite material.The temperature of the drying is 40~50
℃。
The above-mentioned graphene composite material with aggregation-induced emission effect, item existing for the polymer shown in Formulas I
Under part, by the in-situ reducing of graphene oxide, the non-covalent bond modification of graphene is realized, it is multiple to obtain graphene-polymer
Condensation material；The graphene composite material has apparent AIE effect, and the AIE effect of higher molecular itself is strong, and when state of aggregation is glimmering
Light strength ratio is 25 times high in the solution.
It is a kind of above-mentioned for quickly detecting the preparation method of the fluorescent test paper of explosive, including by graphene composite material
Being dissolved in solvent concentration is made is 1 × 10-3~1 × 10-5The solution of mol/L impregnates test paper ontology in acquired solution, after take
Out, it is drying to obtain.
The test paper ontology is unstressed configuration brightening agent test paper.
The solvent is the mixed solvent that water and tetrahydrofuran are mixed to form；The volume of the in the mixed solvent tetrahydrofuran
Percentage is 1%~10%.
The time of the dipping is 8~12min.
A method of it drips using the quick detection explosive of above-mentioned fluorescent test paper, including by testing liquid described glimmering
It is infiltrated in testing liquid on light test paper or by the fluorescent test paper, is taken out after standing, observe fluorescence under 365nm ultraviolet light
The fluorescence intensity change of test paper or the fluorescence intensity change that fluorescent test paper is detected using sepectrophotofluorometer；Work as testing liquid
When containing explosive, fluorescence intensity can be observed and be substantially reduced.
The explosive is explosive containing nitro；The explosive is specially 2,4-DNT, 2,4,6- trinitro-
Toluene, p-nitrophenol, para-nitrotoluene, any one or combination in nitromethane.
The time of the standing is 3~8min.
It is of the invention for quickly detecting the fluorescent test paper of explosive, when contactless nitro explosive (such as picric acid)
Emit green fluorescence under 365nm ultraviolet lamp, its fluorescent quenching after the solution containing nitro explosive contacts test paper, fluorescence intensity
Variation is obvious, and detection process naked eyes are visible.
Fluorescent test paper for quickly detection explosive of the invention, is green fluorescence under 365nm ultraviolet light, contact contains
After the liquid of nitro explosive, fluorescence intensity is reduced, it can be achieved that the quick naked eyes of explosive (especially picric acid) detect；Through
Detection, detection range is wide, precision is high；Method using fluorescent test paper detection explosive is easy to operate, at low cost, it can be achieved that right
The fast qualitative detection of explosive.
When practical application, testing liquid can directly be dripped and be detected on fluorescent test paper, it can also be according to circumstances by testing liquid
It is detected again after appropriate concentration.
Detailed description of the invention
Fig. 1 is the uv absorption spectra of the graphene composite material (rGO-P1) of polymer P 1 and embodiment 1；Wherein A
For using THF as solvent, concentration is 1 × 10-5The uv absorption spectra of mol/L；B is the ultraviolet titration of rGO-P1 under various concentration
Figure, 13.3~40 μ g/mL of concentration range；
Fig. 2 is transmission electron microscope (TEM) figure of the graphene composite material (rGO-P1) of embodiment 1；
Fig. 3 is scanning electron microscope (SEM) figure of the graphene composite material (rGO-P1) of embodiment 1；
Fig. 4 is the thermogravimetric analysis figure of the graphene composite material (rGO-P1) of embodiment 1；
Fig. 5 is the rGO-P1 of embodiment 3 and the fluorescence spectra (concentration: 1 × 10 of polymer P 1-5Mol/L, solvent: THF/
H2O=1/9), right side illustration is photo of the rGO-P1 and P1 solution under 365nm ultraviolet lamp in figure；
When Fig. 6 is bitter taste acid content difference, the variation of the rGO-P1 fluorescence spectrum of embodiment 1；
Fig. 7 is fluorescence intensity change of the fluorescent test paper of embodiment 1 before and after contacting containing picric acid (5ppm) testing liquid；
Fig. 8 is fluorescence intensity change of the fluorescent test paper of embodiment 2 before and after contacting containing picric acid (9ppm) testing liquid.
Specific embodiment
The present invention is further illustrated With reference to embodiment.
In specific embodiment, the polymer with aggregation-induced emission effect, general structure is as shown in following formula I:
In Formulas I, n is 8~20；R1、R2It is independently selected from C1~C6Alkyl, C1~C6Alkoxy or hydrogen.Wherein,
The alkyl can be straight chained alkyl or the alkyl with branch；The alkoxy can be unbranched alkoxy or the alcoxyl with branch
Base.
The synthesis of polymer shown in Formulas I with aggregation-induced emission effect uses Suzuki method, and synthetic route relates to
And reaction equation it is as follows:
The preparation method of above-mentioned polymer, including the following steps:
1) in zinc powder, TiCl4Under the conditions of existing, 4,4 '-dibromobenzo-phenones are dissolved in solvent with compound 1 and are carried out
Compound 2 is made in back flow reaction, separating-purifying；Compound 1, the structural formula of compound 2 are as follows:
2) under the conditions of existing for alkaline matter, the palladium catalyst, compound 2, connection boric acid pinacol ester are added in solvent
It is reacted, separating-purifying obtains compound 3；The structural formula of compound 3 is as follows:
3) under the conditions of existing for alkaline matter, the palladium catalyst, by 3,6- dibromo carbazole, compound 3 be added in solvent into
Row reaction, separating-purifying obtain polymer shown in Formulas I.
One of which has the polymer of aggregation-induced emission effect, shown in the following P1 of structural formula:
The reaction equation that synthetic route is related to is as follows:
The preparation method of polymer P 1, specifically comprises the following steps:
1) synthesis of compound 2-1: taking zinc powder (11.345g, 0.1735mol) to be placed in 250mL reaction tube, takes out ventilation three
It after secondary, is added anhydrous THF (100mL), TiCl is added dropwise under ice bath4(9.11mL, 86.76mmol), is added dropwise after being warmed to room temperature
Be heated to reflux 2h, by 4,4 '-dibromobenzo-phenones (7.375g, 21.69mmol) and 4- butoxy benzophenone (compound 1-1,
5.512g, 21.69mmol) it is dissolved in anhydrous THF (30mL) and is transferred in reaction system, back flow reaction is overnight；After reaction
It is as cold as room temperature, is quenched and is reacted with solution of potassium carbonate, filtering washs filter cake for several times with methylene chloride, filtrate extracts through methylene chloride
After merge organic phase, be spin-dried for solvent, with chloroform/petroleum ether (1/20, v/v) be eluent, through silica gel column chromatography separation mention
After pure, 40 DEG C of dryings are placed in a vacuum drying oven to constant weight, obtain faint yellow viscous oil-like liquid 3.451g, as compound 2-1,
Yield is 27.19%.
The analysis data of compound 2-1 are as follows:1H NMR(CDCl3, 400MHz) δ (TMS, ppm)=7.21~7.28 (m,
4H, Ar-H)；1.45~1.54 (m, 2H ,-CH2CH3)；1.72~1.79 (m, 2H ,-CH2CH2CH2-)；3.92 (t, J=
13.2Hz, 2H ,-OCH2-)；6.65 (d, J=2.0Hz, 2H, Ar-H)；6.67~6.92 (m, 6H, Ar-H)；7.01~7.03
(m, 2H, Ar-H)；7.11~7.15 (m, 3H, Ar-H)；0.99 (t, J=14.8Hz, 3H ,-CH3)。13C NMR(CDCl3,
100MHz) δ (TMS, ppm)=158.0；143.3；142.5；141.9；137.3；135.1；132.9；132.4；131.2；
131.0；130.9；127.7；126.8；120.4；113.7；67.56；31.35；19.26；13.8.
2) synthesis of compound 3-1: taking compound 2-1 (3.502g, 6.23mmol), connection boric acid pinacol ester (3.953g,
15.56mmol), potassium acetate (3.66g, 37.36mmol), (1,1'- bis- (diphenylphosphino) ferrocene) palladium chloride
(0.137g, the 3% of compound 2-1 mole) is placed in dry reaction tube, and after taking out ventilation three times, anhydrous and oxygen-free is added
Isosorbide-5-Nitrae-dioxane (45mL) is stirred overnight reaction under the conditions of 80 DEG C under argon gas protection；End of reaction pours into the two of 200mL
In secondary distilled water, the extraction of 3 × 40mL ethyl acetate (is extracted 3 times, use ethyl acetate 40ml every time), merges organic phase, anhydrous
After magnesium sulfate is dry, filtering, with ethyl acetate/n-hexane (1/15, v/v) for eluent, after silica gel column chromatography separating-purifying,
40 DEG C of dryings are placed in a vacuum drying oven to constant weight, obtain white powder 1.3473g, as compound 3-1, yield 32.96%.
The analysis data of compound 3-1 are as follows: m.p.180-182 DEG C；1H NMR (400MHz, CDCl3) δ (TMS, ppm)=
(7.51-7.57 m, 4H, Ar-H)；(7.08-7.11 m, 3H, Ar-H)；(7.02-7.04 m, 6H, Ar-H)；6.92 (dd, J1=
2.0Hz, J2=7.4Hz, 2H, Ar-H)；6.62 (dd, J1=2.0Hz, J2=8.2Hz, 2H, Ar-H)；3.9 (t, J=6.4Hz,
2H ,-OCH2-)；1.71-1.78 (m, 2H ,-CH2CH2CH2-)；1.44-1.53 (m, 2H ,-CH2CH3)；1.34 (s, 24H ,-
CH3)；0.965 (t, J=7.2Hz, 3H ,-CH2CH3)。
3) synthesis of polymer P 1: be added in 50 milliliters of Schelenk pipes 3,6- dibromo carbazole (390mg, 1.2mmol),
Compound 3-1 (787.8mg, 1.2mmol), potassium carbonate (1.66g, 12mmol), tetra-triphenylphosphine palladium (70mg, 3,6- dibromo clicks
The 5% of azoles mole), logical nitrogen is vacuumized, after replacing 3 times, deoxidation distilled water (8mL), anhydrous THF (24mL), heating is added
It is reacted 3 days to 60 DEG C；After reaction, reaction solution is cooled to room temperature, and a large amount of methanol are added, and has solid precipitation, collects after filtering solid
Body；It after filter cake is dissolved with a small amount of THF, is added drop-wise in a large amount of methanol, crosses filter solid, repeat aforesaid operations three times；It will finally collect
Solid be placed in vacuum oven, be heated to 40 DEG C and be dried overnight, obtain yellow solid 580mg, as polymer P 1, yield
It is 85%.
The analysis data of resulting polymers are as follows: Mw=5962, Mw/Mn=1.30.1H NMR(CDCl3,400MHz)δ
(TMS,ppm):8.78(Ar-H),7.79(Ar-H),7.61(Ar-H),7.53(Ar-H),7.33(Ar-H),6.93(Ar-H),
4.05(-OCH2-),1.82(-CH2-),1.57(-CH2-),1.06(-CH3).13C NMR(CDCl3,100MHz),δ(TMS,
ppm):158.1,144.6,144.5,143.6,142.4,140.6,139.8,136.2,132.0,131.4,129.1,128.1,
126.7,126.2,125.0,124.1,118.8,114.0,111.7,67.5,31.4,19.2,13.6。
Another kind has the polymer of aggregation-induced emission effect, shown in the following P2 of structural formula:
The reaction equation that synthetic route is related to is as follows:
The preparation method of polymer P 2, specifically comprises the following steps:
1) synthesis of compound 2-2: taking zinc powder (10.4g, 0.1735mol) to be placed in 250mL reaction tube, takes out ventilation three times
Afterwards, it is added anhydrous THF (100mL), TiCl is added dropwise under ice bath4(8.79mL, 80mmol) is added dropwise after being warmed to room temperature and heats back
Flow 2h, by 4,4 '-dibromobenzo-phenones (6.8g, 20mmol) and 4,4 '-dibutoxy benzophenone (compound 2-1,
6.529g, 20mmol) it is dissolved in anhydrous THF (30mL) and is transferred in reaction system, back flow reaction is overnight；It is as cold as after reaction
Room temperature is quenched with solution of potassium carbonate and is reacted, and filtering washs filter cake for several times with methylene chloride, filtrate is closed after methylene chloride extracts
And organic phase, it is spin-dried for solvent, with chloroform/petroleum ether (1/20, v/v) for eluent, after silica gel column chromatography separating-purifying,
40 DEG C of dryings are placed in a vacuum drying oven to constant weight, obtain compound 2-2 (3.005g, yield 23.68%).
2) synthesis of compound 3-2: taking compound 2-2 (3.489g, 5.5mmol), connection boric acid pinacol ester (3.491g,
13.75mmol), potassium acetate (3.239g, 33mmol), (1,1'- bis- (diphenylphosphino) ferrocene) palladium chloride (0.120g,
The 3% of compound 2-2 mole) it is placed in dry reaction tube, after taking out ventilation three times, Isosorbide-5-Nitrae-dioxy of anhydrous and oxygen-free is added
Six rings (45mL) are stirred overnight reaction under the conditions of 80 DEG C under argon gas protection；End of reaction pours into the secondary distilled water of 200mL
In, the extraction of 3 × 40mL ethyl acetate (extracts 3 times, use ethyl acetate 40ml every time), merges organic phase, and anhydrous magnesium sulfate is dry
After dry, filtering is that eluent is placed in vacuum after silica gel column chromatography separating-purifying with ethyl acetate/n-hexane (1/15, v/v)
40 DEG C of dryings obtain compound 3-2 (1.32g, yield 36.56%) to constant weight in drying box.
3) synthesis of polymer P 2: be added in 50 milliliters of Schelenk pipes 3,6- dibromo carbazole (487.5mg,
1.5mmol), compound 3-2 (984.7mg, 1.5mmol), potassium carbonate (2.073g, 15mmol), tetrakis triphenylphosphine palladium
(52mg, the 3% of 3,6- dibromo carbazole moles) vacuumizes logical nitrogen, and after replacing 3 times, deoxidation distilled water (8mL), nothing is added
Water THF (24mL) is heated to 60 DEG C and reacts 3 days；After reaction, reaction solution is cooled to room temperature, and a large amount of methanol are added, and has solid analysis
Out, solid is collected after filtering；It after filter cake is dissolved with a small amount of THF, is added drop-wise in a large amount of methanol, crosses filter solid, repeat aforesaid operations
Three times；Finally the solid of collection is placed in vacuum oven, 40 DEG C is heated to and is dried overnight, obtain polymer P 2
(409.5mg, yield 64%).
In specific embodiment, the size of test paper ontology is identical as pH test paper, is the test strips of 60mm × 10mm.
Embodiment 1
The present embodiment is used for the quick fluorescent test paper for detecting explosive, including test paper ontology, bears on the test paper ontology
It is loaded with graphene composite material, the graphene composite material includes graphene and polymer P 1, and polymer P 1 is with non-covalent bond
Form is grapheme modified.
The preparation method of the fluorescent test paper for quickly detecting explosive of the present embodiment, comprising the following steps:
1) graphene composite material is prepared:
A) it takes 10mg graphene oxide (GO), is added in THF (10mL), ultrasonic 20min makes it be uniformly dispersed, and is aoxidized
Graphene dispersing solution；
Polymer P 1 (100mg) is taken, is dissolved in THF (20mL), obtains polymer solution；
B) graphene oxide dispersion obtained by step a) is added drop-wise in resulting polymers solution with constant pressure funnel (poly-
The mass ratio for closing object and graphene oxide is 10:1), it after stirring 2h, is added hydrazine hydrate (0.25mL), back flow reaction 8h, reaction knot
Obtained black uniform solution is cooled to room temperature by Shu Hou, and (8000rpm, 30min) is centrifugated after ultrasonic 20min and obtains supernatant
Liquid, after solvent is removed under reduced pressure in supernatant, obtained solid is placed in a vacuum drying oven 45 DEG C and is dried overnight to get graphene composite wood
Expect (being denoted as rGO-P1)；
2) using the volume ratio of water and tetrahydrofuran for 90:10 mixture as solvent, by gained graphene composite material
(rGO-P1) being dissolved in solvent concentration is made is 1 × 10-3Test paper ontology is impregnated 10min by the solution of mol/L in acquired solution,
After take out, dry up to the fluorescent test paper；
Gained fluorescent test paper is the fluorescent test paper strip for having green-fluorescent emission under 365nm ultraviolet lamp.
The bitter taste aqueous acid that preparation concentration is 5ppm in advance is testing liquid.
The method of the quick detection explosive using above-mentioned fluorescent test paper of the present embodiment, including by gained fluorescent test paper
It is infiltrated in testing liquid, is taken out after standing 5min, the fluorescence intensity change of fluorescent test paper is observed under 365nm ultraviolet lamp or adopt
With fluorescence intensity change of the sepectrophotofluorometer detection fluorescent test paper at 490~500nm；The fluorescence intensity of fluorescent test paper is bright
It is aobvious to reduce, judge that testing liquid contains explosive.
Embodiment 2
The present embodiment is used for the quick fluorescent test paper for detecting explosive, including test paper ontology, bears on the test paper ontology
It is loaded with graphene composite material, the graphene composite material includes graphene and polymer P 2, and polymer P 2 is with non-covalent bond
Form is grapheme modified.
The preparation method of the fluorescent test paper for quickly detecting explosive of the present embodiment, comprising the following steps:
1) graphene composite material is prepared:
A) it takes 5mg graphene oxide (GO), is added in THF (50mL), ultrasonic 40min makes it be uniformly dispersed, and is aoxidized
Graphene dispersing solution；
Polymer P 2 (25mg) is taken, is dissolved in THF (5mL), obtains polymer solution；
B) graphene oxide dispersion obtained by step a) is added drop-wise in resulting polymers solution with constant pressure funnel (poly-
The mass ratio for closing object and graphene oxide is 5:1), it after stirring 2h, is added hydrazine hydrate (0.13mL), back flow reaction for 24 hours, reacts knot
Obtained black uniform solution is cooled to room temperature by Shu Hou, and (11000rpm, 10min) is centrifugated after ultrasonic 40min and obtains supernatant
Liquid, after solvent is removed under reduced pressure in supernatant, obtained solid is placed in a vacuum drying oven 45 DEG C and is dried overnight to get graphene composite wood
Material；
2) using the volume ratio of water and tetrahydrofuran for 95:5 mixture as solvent, gained graphene composite material is dissolved in
It is 1 × 10 that concentration, which is made, in solvent-4Test paper ontology is impregnated in acquired solution 10min, takes out, dried i.e. afterwards by the solution of mol/L
Obtain the fluorescent test paper.
Gained fluorescent test paper is the fluorescent test paper strip for having green-fluorescent emission under 365nm ultraviolet lamp.
The bitter taste aqueous acid that preparation concentration is 10ppm in advance is testing liquid.
The method of the quick detection explosive using above-mentioned fluorescent test paper of the present embodiment, including by gained fluorescent test paper
It is infiltrated in testing liquid, is taken out after standing 5min, the fluorescence intensity change of fluorescent test paper is observed under 365nm ultraviolet lamp or adopt
With fluorescence intensity change of the sepectrophotofluorometer detection fluorescent test paper at 490~500nm；The fluorescence intensity of fluorescent test paper is bright
It is aobvious to reduce, judge that testing liquid contains explosive.
Embodiment 3
The present embodiment is used for the quick fluorescent test paper for detecting explosive, including test paper ontology, bears on the test paper ontology
It is loaded with graphene composite material, the graphene composite material includes graphene and polymer P 1, and polymer P 1 is with non-covalent bond
Form is grapheme modified.
The preparation method of the fluorescent test paper for quickly detecting explosive of the present embodiment, comprising the following steps:
1) graphene composite material is prepared:
A) it takes 10mg graphene oxide (GO), is added in THF (20mL), ultrasonic 60min makes it be uniformly dispersed, and is aoxidized
Graphene dispersing solution；
Polymer P 1 (80mg) is taken, is dissolved in THF (16mL), obtains polymer solution；
B) graphene oxide dispersion obtained by step a) is added drop-wise in resulting polymers solution with constant pressure funnel (poly-
The mass ratio for closing object and graphene oxide is 8:1), it after stirring 2h, is added hydrazine hydrate (0.25mL), back flow reaction 12h, reaction knot
Obtained black uniform solution is cooled to room temperature by Shu Hou, and (9000rpm, 20min) is centrifugated after ultrasonic 30min and obtains supernatant
Liquid, after solvent is removed under reduced pressure in supernatant, obtained solid is placed in a vacuum drying oven 45 DEG C and is dried overnight to get graphene composite wood
Material；
2) using the volume ratio of water and tetrahydrofuran for 99:1 mixture as solvent, gained graphene composite material is dissolved in
It is 1 × 10 that concentration, which is made, in solvent-5Test paper ontology is impregnated in acquired solution 10min, takes out, dried i.e. afterwards by the solution of mol/L
Obtain the fluorescent test paper.
Gained fluorescent test paper is the fluorescent test paper strip for having green-fluorescent emission under 365nm ultraviolet lamp.
The bitter taste aqueous acid that preparation concentration is 9ppm in advance is testing liquid.
The method of the quick detection explosive using above-mentioned fluorescent test paper of the present embodiment, including by gained fluorescent test paper
It is infiltrated in testing liquid, is taken out after standing 5min, the fluorescence intensity change of fluorescent test paper is observed under 365nm ultraviolet lamp or adopt
With fluorescence intensity change of the sepectrophotofluorometer detection fluorescent test paper at 490~500nm；The fluorescence intensity of fluorescent test paper is bright
It is aobvious to reduce, judge that testing liquid contains explosive.
In specific embodiment, graphene oxide used (GO) is purchased from Nanjing Xian Feng nanosecond science and technology Co., Ltd, at it
In his embodiment, it can also be prepared using graphite as raw material by Hummers oxidation.
Experimental example 1
The graphene composite material (being denoted as rGO-P1) of embodiment 1 is detected, wherein the content of graphene (rGO) is
16.2%.The rGO-P1 dissolves in organic solvent, in tetrahydrofuran (THF), n,N-Dimethylformamide (DMF), N- methyl pyrrole
There is preferable dissolubility in the organic solvents such as pyrrolidone (NMP).When using THF as solvent (as shown in Figure 1), the ultraviolet suction of rGO-P1
It receives peak and is located at 255 and 312nm, when its concentration is 13.3~40 μ g/mL, fluorescence intensity is in a linear relationship with solution concentration, table
Bright rGO-P1 has dissolubility good in THF.
Fig. 2, Fig. 3 are respectively the transmission electron microscope picture and scanning electron microscope (SEM) photograph of the graphene composite material (rGO-P1) of embodiment 1.
From Fig. 2,3 it is apparent that after non-covalent bond modification, graphene is wrapped up by macromolecule, just because of this package effect
And π-π interaction, so that the dissolubility of graphene composite material greatly improves.
Fig. 4 is the thermogravimetric analysis figure of the graphene composite material (rGO-P1) of embodiment 1.By calculating the composite material surveyed
The content of middle rGO is 16.2%.
Experimental example 2
This experimental example measures the glimmering of 3 gained graphene composite material (rGO-P1) of embodiment using water and THF as mixed solvent
Luminous intensity.Its fluorescence intensity (as shown in Figure 5) is measured using water and THF as mixed solvent, the rGO-P1 when water content is 90%
Fluorescence is 25.7 times of initial strength, and fluorescence emission wavelengths are located at 497.6nm or so, is in the UV lamp bright blue green light；
Under equal conditions, P1 is 5.7 times of green strength, this shows that graphene composite material prepared by the present invention has AIE effect,
And it is more significant compared with P1.
Experimental example 3
This experimental example detects the fluorescence spectrum of the graphene composite material (rGO-P1) of embodiment 1, and picric acid contains
When measuring different, the fluorescence spectrum variation of the graphene composite material (rGO-P1) of embodiment 1 is as shown in Figure 6.It can from Fig. 6
Out, with the increase of bitter taste acid content, the fluorescence intensity of solution is gradually decreased, glimmering when bitter taste acid concentration is 15.57ppm
Light is almost quenched completely, and minimum response concentration is 1.3ppb；When bitter taste acid concentration is lower than 0.21ppm, the drop of fluorescence intensity
It is low in a linear relationship with picric content, constant is quenched and is up to 4.16 × 106M-1, higher than reported based on AIE molecule
Fluorescence detector；In the concentration range of 0.3~3.3ppm, the reduction of fluorescence intensity and picric content are in a linear relationship,
Constant is quenched and is up to 1.09 × 106M-1.This shows that rGO-P1 has preferable fluorescence response to picric acid, is particularly suitable for bitter taste
The trace detection of acid.
The Strength Changes difference of embodiment 1 and 2 gained fluorescent test paper of embodiment before and after contacting testing liquid containing picric acid
As shown in Figure 7, Figure 8.It can be seen from the figure that fluorescence intensity change of the present invention gained fluorescent test paper before and after contacting picric acid
Significantly, it can be achieved that the quick naked eyes of explosive detect.
Claims (10)
1. a kind of for quickly detecting the fluorescent test paper of explosive, it is characterised in that: including test paper ontology, on the test paper ontology
Load has a graphene composite material, and the graphene composite material includes polymer shown in graphene and Formulas I, shown in Formulas I
Polymer is grapheme modified in the form of non-covalent bond；The graphene composite material is under the polymer existence condition shown in Formulas I,
Made of the in-situ reducing of graphene oxide；
In Formulas I, n is 8~20；R1、R2It is independently selected from C1~C6Alkyl, C1~C6Alkoxy or hydrogen.
2. according to claim 1 for quickly detecting the fluorescent test paper of explosive, it is characterised in that: in Formulas I, R1、R2Respectively
Methyl, ethyl, butyl, hexyl, methoxyl group, ethyoxyl, butoxy, hexyloxy or hydrogen are selected from from independent.
3. according to claim 1 for quickly detecting the fluorescent test paper of explosive, it is characterised in that: gather shown in Formulas I
The mass ratio for closing object and forming the graphene oxide of graphene is 5~10:1.
4. according to claim 3 for quickly detecting the fluorescent test paper of explosive, it is characterised in that: the graphene is multiple
Condensation material is prepared by method comprising the following steps:
A) polymer solution is made in polymer shown in Formulas I；
B) graphene oxide dispersion is mixed with polymer solution, be added hydrazine hydrate back flow reaction, after reaction through ultrasound,
Centrifuge separation takes supernatant to remove solvent, be drying to obtain.
5. a kind of as described in claim 1 for quickly detecting the preparation method of the fluorescent test paper of explosive, it is characterised in that:
It is 1 × 10 including graphene composite material to be dissolved in solvent concentration is made-3~1 × 10-5The solution of mol/L exists test paper ontology
It is impregnated in acquired solution, takes out, is drying to obtain afterwards.
6. according to claim 5 for quickly detecting the preparation method of the fluorescent test paper of explosive, it is characterised in that: institute
Stating solvent is the mixed solvent that water and tetrahydrofuran are mixed to form；The percent by volume of the in the mixed solvent tetrahydrofuran is
1%~10%.
7. according to claim 5 for quickly detecting the preparation method of the fluorescent test paper of explosive, it is characterised in that: institute
The time for stating dipping is 8~12min.
8. a kind of method of the quick detection explosive using fluorescent test paper as described in claim 1, it is characterised in that: including
Testing liquid drop is infiltrated in testing liquid on the fluorescent test paper or by the fluorescent test paper, is taken out after standing,
The fluorescence intensity change of fluorescent test paper is observed under 365nm ultraviolet light or using the glimmering of sepectrophotofluorometer detection fluorescent test paper
Intensity variation；When testing liquid contains explosive, fluorescence intensity can be observed and be substantially reduced.
9. the method for quick detection explosive according to claim 8, it is characterised in that: the explosive is 2,4,6- tri-
Nitrophenol, 2,4-DNT, 2,4,6- trinitrotoluene, p-nitrophenol, para-nitrotoluene, appointing in nitromethane
It anticipates a kind of or combines.
10. the method for quick detection explosive according to claim 8 or claim 9, it is characterised in that: the time of the standing is
3~8min.
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