CN107488147A - A kind of fluorescence probe and preparation method and application - Google Patents
A kind of fluorescence probe and preparation method and application Download PDFInfo
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- CN107488147A CN107488147A CN201710727212.3A CN201710727212A CN107488147A CN 107488147 A CN107488147 A CN 107488147A CN 201710727212 A CN201710727212 A CN 201710727212A CN 107488147 A CN107488147 A CN 107488147A
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- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The present invention relates to a kind of fluorescence probe and preparation method and application, belong to technical field of analysis and detection.The fluorescence probe of the present invention has the structural formula as shown in formula (I).The fluorescence probe of the present invention can specific recognition isocyanates, and after the fluorescence probe reacts with isocyanate ester compound, blue shift occurs for its fluorescence emission wavelengths, therefore the fluorescence probe can realize the Ratio-type fluoroscopic examination to isocyanate ester compound, the detection and analysis for isocyanates in liquid environment, air ambient, chemical example etc..Fluorescence probe good light stability of the present invention, and it detects the specificity of isocyanate ester compound, sensitivity and selectivity height.
Description
Technical field
The present invention relates to a kind of fluorescence probe and preparation method and application, and in particular to one kind is used to detect isocyanates
Fluorescence probe of class compound and preparation method and application, belongs to technical field of analysis and detection.
Background technology
Isocyanates is the organic compound that a major class contains NCO (- N=C=O).It common are；2- chloroethenes
Based isocyanate (2-chloroethyl isocyanate, CEI), toluene di-isocyanate(TDI) (TDI), there are two kinds of isomerisms
Body (2,4-TDI and 2,6-TDI)；Methyl diphenylene diisocyanate MDI, 1,6- second diisocyanate (Hexamethylene
Diisocyanate, HDI) and IPDI IPDI etc..Wherein, toluene di-isocyanate(TDI) (TDI) and diphenyl
Methane diisocyanate (MDI) yield highest, it is most widely used.NCO is a kind of height unsaturated group, is had very high
Reactivity, can be reacted with organic matter of the multiclass containing active hydrogen.
Harm of the isocyanates type organic to organism is many.Isocyanates is gentle with vaporous in atmosphere
The form of dissolved colloidal state is present, and mainly enters organism in the form of two kinds of breathing and skin contact.Respiratory tract contacts isocyanates meeting
Produce the bronchitis even symptom such as asthma；Skin infection even allergic dermatitis can be produced after skin contact to be difficult to cure；
After eye contact can stimulating organism body eye mucous membranes, eye conjunctivitis can be produced by shouting pain symptom, the severe patient such as shed tears occur；Isocyanide
Acid esters type organic has a certain impact to the hematopoiesis function of human body, the staff's for being partly engaged in polyurethane production and scientific research
Platelet count has to be reduced to a certain degree；If be chronically in the environment of isocyanates type organic of higher concentration, human body
Heart and central nervous system can be by different degrees of infringements；The more seriously meeting of isocyanates type organic and biological cell
Middle macromolecular reacts, and causes organism base to be exchanged, framework variation, or even chromosome deficiency.Therefore, it is sensitive, reliable
The detection of isocyanate ester compound is significant.
So far, detection of the domestic and international researcher to hydrogen sulfide has carried out substantial amounts of research.It is developed so far and compares into
Ripe specific method has AAS, gas chromatography, high performance liquid chromatography etc..AAS is to be based on different samples
Different colors is presented in concentration, and causes materials absorbed light degree different, and a kind of detection method being measured.Spectrophotometer with
Other instruments are compared, easy to use, simple to operate, cheap, and developer used, which also compares, to be easy to get, and cost is relatively low.Isocyanide
The conventional AAS of acid esters type organic have n-butylamine-malachite green spectrophotometery, hydrochloride naphthodiamide AAS,
Three kinds of paradime thylaminobenzaldehyde method.The third method has relatively high accuracy and reliability compared with first two, and first two side
Method can be had a strong impact on Detection results by the endless fully hydrolyzed limitation of isocyanates.Therefore, although AAS operation letter
It is single but larger to the demand of laboratory sample；The unstability of developing time and color developing effect also can cause shadow to Detection results
Ring；AAS can only detect total isocyanates, and the content of one of which isocyanates can not be carried out plus surveyed, practical
Property is relatively low.Gas chromatography has higher sensitivity and accuracy, and selectivity is high and analyze speed is fast.National standard to TDI and
MDI detection method is detected using electron capture detector (ECD), and ECD is higher to the responsiveness of halogen compounds.
First TDI and MDI is hydrolyzed in acid condition to obtain the ammonium of toluene two (TDA) and MDA (MDA), Ran Houjing
Heptafluorobutyric anhydride is detected after deriving.There is research to have using hydrogen flame ionization detector (FID) directly measure isocyanates
Although the content of machine thing, this method do not need derivation operation, but higher to the eyeball of chromatographic column, it would be desirable to be able to TDI isomery
Body and MDI are separated.Therefore, though the isocyanates detection that gas chromatography is current comparative maturity is provided, to experiment
Operability requires very high, the content of isocyanates can only be detected in laboratory, the requirement to place is very high, it is impossible to full
Foot can determine the requirement of isocyanate content in any place, and practicality is only limitted to laboratory, it is impossible to for popular, factory and work
Ground is used.The gas chromatography most important is that isocyanates type organic gasifies, and the boiling point of isocyanates
Higher, the higher isocyanates that can make polymerization of temperature of gasification is degraded, so as to directly affect the Detection results of isocyanates.
The principle of isocyanate concentration is to react isocyanates and derivating agent, obtain in high performance liquid chromatography (HPLC) measure air
To stable derivative, concentrated processing or direct injection analysis, result is obtained.It is easy to and water and alcohol generation using isocyanates
Reaction, so after the derivative stablized, then it is a kind of more conventional detection side to carry out detection with high performance liquid chromatograph
Method.Improved by multidigit researcher years of researches, make the HPLC methods of derivating agent using 2PP, to the isocyanates of mixing
Separating effect is excellent, high sensitivity, can carry out qualitative analysis and quantitative detection, may turn into the routine of isocyanates from now on
Detection means.Wu etc. makees derivating agent with tryptamines, establishes glimmering photo-electrochemical double check method, and the toluene of tryptamines is contained with impact tube
Solution samples, and HPTC separation, using fluoroscopic examination as quantitative basis, effectively a variety of isocyanates and its polymer can be examined
Survey.Although liquid chromatography is fine to the Detection results of isocyanates, separating degree and accuracy are high, and operability is high, cost is high,
It is unfavorable for popularizing routine testing.
In a word, the method for current comparative maturity has its advantage and disadvantage, the low AAS accuracy of cost simple to operate
Not high, using effect is low；Although gas chromatography and liquid chromatography Detection results are outstanding, derivative step is needed to cause it
Operation development, cost is higher, is unfavorable for daily Site Detection.
The content of the invention
There is provided a kind of for detecting isocyanates it is an object of the invention to overcome above-mentioned the deficiencies in the prior art part
Fluorescence probe of class compound and preparation method and application.
To achieve the above object, the technical scheme taken of the present invention is：
In a first aspect, the invention provides a kind of fluorescence probe, it has the structural formula as shown in formula (I)：
The above-mentioned fluorescence probe of the present invention is N- normal-butyls -6- hydroxyls-anthracene acid imide, and its molecular formula is C49H39N7O7, phase
It is 318.11 to molecular mass.The fluorescence probe is the tasteless solid powder of peony, is dissolved in water, is soluble in methanol, ethanol, solvable
In chloroform equal solvent.
Stable Intramolecular electron transfer can occur for the fluorescence probe of the present invention, and the supplied for electronic amino in N- positions can turn
Electronics is moved to the electrophilic hydroxyl on 6- positions；The phenolic hydroxyl group of fluorescence probe 6- positions visible region without absorb, also do not send out
Fluorescence is penetrated, and it contains active hydrogen, can be used as recognition group.The recognition group described in alcohol system easily with isocyanates
Esterification occurs for the NCO in compound, forms ester group, so as to cause the electron-withdrawing power of 6- positions group to become strong, leads
The original Intramolecular electron transfer balance of fluorescence probe is caused to change, blue shift occurs for its fluorescence emission wavelengths, fluorescence probe
Fluorescence is changed into gold-tinted from feux rouges.Increase with the content of isocyanates, red fluorescence weakens, orange fluorescence enhancing, red glimmering
The ratio of light and orange fluorescence can be used as detection signal, therefore the probe can realize the Ratio-type to isocyanate ester compound
Fluoroscopic examination.
Research shows, in methanol solution, N- normal-butyls -6- hydroxyls-anthracene acid imide before being reacted with isocyanates,
522nm's excites under light irradiation, launches red fluorescence in 596nm or so；Phenol in N- normal-butyls -6- hydroxyls-anthracene acid imide
After hydroxyl reacts with NCO, its phenolic hydroxyl group recognition group is changed into ester group with NCO reaction, and thus it can inhale
Receive 522nm or so exciting light, and launch orange fluorescence in 560nm or so, therefore red fluorescence weakens, acceptor emission it is orange
Color Fluorescence Increasing.
Above-mentioned photoluminescent property based on fluorescence probe of the present invention, its can specific recognition isocyanate ester compound, be used for
The detection and analysis of isocyanate ester compound in biological sample, environmental sample, chemical example etc..Also, the fluorescence of the present invention is visited
Pin good light stability, detection are quick.
Second aspect, the invention provides a kind of preparation method of above-mentioned fluorescence probe, it comprises the following steps：
(1) using 9- bromines anthracene and oxalyl chloride as raw material, 6- bromine of the acylation reaction preparation structure formula as shown in formula (∏) is passed through
Aceanthrylene -1,2- diketone；
(2) 6- bromines aceanthrylene -1,2- diketone made from potassium hydrogen persulfate oxidation step (1), preparation structure formula such as formula are used
(III) the bromo- 1,2 dicarboxyl anthroic acid acid anhydrides of 6- shown in；
(3) with the dicarboxyl anthroic acid acid anhydrides of 6- made from step (2) bromo- 1,2 and n-butylamine for raw material, preparation structure formula such as formula
(IV) the bromo- anthracene acid imides of N- normal-butyls -6- shown in；
(4) using the bromo- anthracene acid imides of N- normal-butyls -6- made from step (3) and sodium methoxide as raw material preparation structure formula such as formula
(V) N- normal-butyls -6- methoxyl groups-anthracene acid imide shown in；
(5) with N- normal-butyls -6- methoxyl groups-anthracene acid imide made from step (4) and acid for raw material, preparation structure formula such as formula
(I) fluorescence probe shown in；
As the preferred embodiment of the preparation method of fluorescence probe of the present invention, the preparation method of the fluorescence probe
Comprise the following steps：
(1) 9- bromines anthracene, oxalyl chloride solution, alchlor and carbon disulfide are mixed, under nitrogen or inert gas shielding, in
After being reacted in 0 DEG C of ice bath, 8-10 hours are reacted under room temperature condition；Then hydrochloric acid is added, in 50 DEG C of reactions；It is finally cooled to
Room temperature, filtering, dry, purified filter solid, obtain 6- bromine aceanthrylene -1,2- diketone；
(2) 6- bromine aceanthrylene -1,2- diketone and potassium hydrogen persulfate are dissolved in methanol, in nitrogen or inert gas shielding
Under reacted；Then reaction product is spin-dried for, is filtered after washing, the solid of purifying filtering gained, obtains 6- bromo- 1,2 dicarboxyls
Anthroic acid acid anhydride；
(3) the dicarboxyl anthroic acid acid anhydrides of 6- bromo- 1,2 and n-butylamine are dissolved in ethanol, under nitrogen or inert gas shielding
Reacted；Ethanol is removed after reaction, the product after ethanol is removed with dichloromethane and water extraction, collects organic phase；Re-dry,
Organic phase is filtered, the obtained rotated evaporation of solvent of filtrate, solid obtained by purifying rotary evaporation, obtains N- normal-butyls -6-
Bromo- anthracene acid imide；
(4) N- normal-butyls -6- bromo- anthracene acid imide, sodium methoxide and mantoquita are dissolved in methanol, in nitrogen or inert gas
Reacted under protection；Methanol is removed after reaction, the product after methanol is removed with dichloromethane and water extraction, collects organic phase；
Re-dry, filtering organic phase, the obtained rotated evaporation of solvent of filtrate, solid obtained by purifying rotary evaporation, are obtaining N- just
Butyl -6- methoxyl groups-anthracene acid imide；
(5) hydroiodic acid is added into N- normal-butyls -6- methoxyl groups-anthracene acid imide, after reaction, adjusts the pH of reaction product
Value, is refiltered, and purifying filtering gained solid, obtains fluorescence probe of the structural formula as shown in formula (I).
As the preferred embodiment of the preparation method of fluorescence probe of the present invention, in step (1)~(5),
Purified using silica gel column chromatography.
As the preferred embodiment of the preparation method of fluorescence probe of the present invention, in the step (1), according to every milli
Mole 9- bromines anthracene adds the ratio of 4~5mL carbon disulfide, and 9- bromine anthracenes are added in carbon disulfide；In the step (2), according to
Every mM of 6- bromine aceanthrylenes -1,2- diketone adds the ratio of 10~23mL methanol, and 6- bromine aceanthrylene -1,2- diketone is added into first
In alcohol；In the step (3), the ratio of 10~23mL ethanol is added according to the dicarboxyl anthroic acid acid anhydrides of every mM of 6- bromo- 1,2, will
The bromo- 1,2 dicarboxyl anthroic acid acid anhydrides of 6- are added in ethanol；It is sub- according to the bromo- anthracene acyls of every mM of N- normal-butyls -6- in the step (4)
Amine adds the ratio of 10~23mL methanol, and the bromo- anthracene acid imides of N- normal-butyls -6- are added in methanol, and the N- normal-butyls -6-
The mol ratio of bromo- anthracene acid imide and mantoquita is 1：0.03~0.05.
The third aspect, the invention provides application of the above-mentioned fluorescence probe in isocyanate ester compound is detected.
Fourth aspect, the invention provides above-mentioned fluorescence probe to prepare the reagent for detecting isocyanate ester compound
Application in box or Test paper.
5th aspect, it is used to detect the kit or Test paper of isocyanate ester compound the invention provides a kind of,
It contains above-mentioned fluorescence probe.
6th aspect, the invention provides a kind of preparation side for being used to detect the Test paper of isocyanate ester compound
Method, it comprises the following steps：
(1) above-mentioned fluorescence probe is dissolved in alcohol, obtains the solution containing the fluorescence probe；
(2) step (1) resulting solution is applied on filter paper or filter paper is dipped into step (1) resulting solution, then will filter
Paper dries, and obtains the Test paper for detecting isocyanate ester compound.
The Test paper of the present invention can be used for the quick detection of isocyanate ester compound in air, only need during detection by
After Test paper is as minute in air ambient, using portable from coat etc., color of the observation test paper under 365nm exciting lights
Conversion it is known that in air isocyanates substantially concentration.
As being preferable to carry out for the preparation method of the present invention for being used to detect the Test paper of isocyanate ester compound
Mode, the alcohol are methanol or ethanol.
Compared with prior art, beneficial effects of the present invention are：
(1) the invention provides a kind of fluorescence probe (N- normal-butyls -6- hydroxyls-anthracene acid imide), the phenol hydroxyl of its 6- position
Base can specific recognition isocyanates, and after the reaction of the fluorescence probe and isocyanate ester compound, its fluorescence emission wavelengths hair
Raw blue shift, therefore the fluorescence probe can realize the Ratio-type fluoroscopic examination to isocyanate ester compound, for liquid environment, sky
The detection and analysis of isocyanates in compression ring border, chemical example etc..Only pass through single launch wavelength compared to on-off type fluorescence probe
Strength Changes detect isocyanate concentration, and fluorescence probe of the invention surveyed by the fluorescence intensity ratio of two wavelength of transmitted light
Isocyanate concentration is tried, is avoided unstable, the insensitive equal error of launch wavelength detection by fluorescence probe concentration, excitation wavelength
Influence.It is difficult the ratio for influenceing two kinds of fluorescence intensities in methanol system that external factor, which is, and this pattern can greatly reduce outside
The influence of factor, improve accuracy of detection and accuracy.
(2) fluorescence probe good light stability of the present invention, and its detect the specificity of isocyanate ester compound, sensitivity and
Selectivity is high, has identical sensitiveness to different types of isocyanates.
(3) using the fluorescence probe detection isocyanate ester compound very rapid and convenient of the present invention：In detection Breakup of Liquid Ring
In border during isocyanate content, a certain amount of detection sample need to be only dissolved in the fluorescence probe solution of certain concentration, test is mixed
The ratio of fluorescence intensity at 560nm and 590nm of liquid is closed, the concentration of isocyanates is converted into by standard curve, and only
Want 30 seconds can total overall reactions complete；In the content of isocyanates in detecting air ambient, it is only necessary to by Test paper extremely
In air ambient after minute, using portable from coat etc., colour switching can of the observation test paper under 365nm exciting lights
Know the substantially concentration of isocyanates in air, and only need can detection in 5 minutes to finish.
(4) preparation technology of fluorescence probe of the present invention is simple, conveniently；The detection architecture of the present invention is easy to use, is easy to push away
Wide application.
Brief description of the drawings
Fig. 1 is the synthetic route chart of fluorescence probe of the present invention；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of 6- bromine aceanthrylene -1,2- diketone in the embodiment of the present invention 1；
Fig. 3 is the mass spectrogram of 6- bromine aceanthrylene -1,2- diketone in the embodiment of the present invention 1；
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of the bromo- 1,2 dicarboxyl anthroic acid acid anhydrides of 6- in the embodiment of the present invention 1；
Fig. 5 is the mass spectrogram of the bromo- 1,2 dicarboxyl anthroic acid acid anhydrides of 6- in the embodiment of the present invention 1；
Fig. 6 is the imido hydrogen nuclear magnetic resonance spectrogram of the bromo- anthracenes of N- normal-butyls -6- in the embodiment of the present invention 1；
Fig. 7 is the imido mass spectrogram of the bromo- anthracenes of N- normal-butyls -6- in the embodiment of the present invention 1；
Fig. 8 is N- normal-butyls -6- methoxyl groups-imido hydrogen nuclear magnetic resonance spectrogram of anthracene in the embodiment of the present invention 1；
Fig. 9 is N- normal-butyls -6- methoxyl groups-imido mass spectrogram of anthracene in the embodiment of the present invention 1；
Figure 10 is the hydrogen nuclear magnetic resonance spectrogram of fluorescence probe of the present invention；
Figure 11 is the carbon-13 nmr spectra figure of fluorescence probe of the present invention；
Figure 12 is the mass spectrogram of fluorescence probe of the present invention；
Figure 13 is fluorescence probe of the present invention and isocyanates reaction and its schematic diagram of change in fluorescence；
Figure 14 is to add the fluorescence spectrum variation diagram after not same amount isocyanates in fluorescence probe of the present invention；
Figure 15 is after adding not same amount isocyanates in fluorescence probe of the present invention, and fluorescence is strong at 560nm and at 596nm for it
Spend the changing trend diagram of ratio；
After Figure 16 is Test paper places 5 minutes in the air containing isocyanates made from embodiment 4, in 365nm
Under uviol lamp, the variation diagram of test paper color；
Figure 17 is that Test paper made from embodiment 4 is comprising only in acetone, toluene, chloroform, ether, acetic acid second respectively
When being detected in ester, propylene and formaldehyde air ambient, under 365nm uviol lamps, the variation diagram of test paper color；
Figure 18 is that Test paper made from embodiment 4 is carried out in 2,4-TDI, 2,6-TDI, MDI, HDI and IPDI environment
Detection, the viewing test result figure under 365nm uviol lamps；
Figure 19 is regression curve of the isocyanates of embodiment 6 (R-NCO) in low strength range.
Embodiment
For the object, technical solutions and advantages of the present invention are better described, below in conjunction with the drawings and specific embodiments pair
The present invention is described further.
Embodiment 1
A kind of embodiment of fluorescence probe of the present invention and preparation method thereof, the fluorescence probe of the present embodiment for N- normal-butyls-
6- hydroxyls-anthracene acid imide, shown in its structural formula such as formula (I),
The synthetic route of the fluorescence probe of the present embodiment is as shown in figure 1, its specific preparation method is as follows：
1) under 0 DEG C of ice bath, nitrogen protection and stirring condition, by 9- bromines anthracene (1.03g, 4mmol) and oxalyl chloride solution
It is anti-then to add alchlor (0.81g, 6mmol) in carbon disulfide (8~10ml) for (1.92ml, 10mmol) stirring and dissolving
Answer 2 hours；Carbon disulfide (8~10ml) and alchlor (0.64g, 4.8mmol) are added, 0 DEG C of ice bath is kept and stirs again
After mixing reaction 2 hours, stirring reaction (8-10) hour under ice bath room temperature condition is removed；Add 1-2M hydrochloric acid solution 60ml and rise
Temperature is kept for 10 minutes to 50 DEG C；After being cooled to room temperature, (sodium hydroxide for using 5-10%w/w again is first washed with water in filtering during filtering
Solution is rinsed and is finally washed with water), crude extract (filter residue) is placed into the drying 48 hours of 50 DEG C of vacuum drying chamber；By the shallow palm fibre of gained
Color solid by silica gel chromatography post purifies to obtain brown solid 6- bromine aceanthrylenes -1,2- diketone (0.93g, yield 75%).Pass through core
Magnetic resonance hydrogen spectrum characterizes to the product, as a result as shown in Fig. 2 being specially：1H NMR(CDCl3,600MHz,ppm):
7.82-7.92 (m, 3H), 8.12 (d, J=6.6Hz, 1H), 8.63 (d, J=6.0Hz, 1H), 8.71 (d, J=6.0Hz, 1H),
9.27 (d, J=6.6Hz, 1H).In addition, secondary proof is carried out by mass spectrum, as a result as shown in figure 3, being specially：MS(ESI):
M/z=310.1 [M+H]+can determine that synthesized product is title intermediate by analysis.
2) under nitrogen protective condition, by 6- bromine aceanthrylene -1,2- diketone (0.93g, 3mmol) and potassium hydrogen persulfate
(2.31g, 15mmol) be dissolved in methanol (30~69ml) be heated to 72 DEG C be stirred at reflux reaction 72 hours；Room temperature is cooled to, is revolved
Washing filtering after dry, and by gained solid by silica gel column chromatography purifying (dichloromethane：Petroleum ether=1：3)；Will be resulting
Product is put into 40 DEG C of dry 8-12 hours in vacuum drying chamber, obtains the bromo- 1,2 dicarboxyl anthroic acid acid anhydrides of sepia solid 6-
(0.86g, yield 85%) is characterized by proton nmr spectra to the product, as a result as shown in figure 4, being specially：1H NMR
(CDCl3,600MHz,ppm):7.85 (t, J=6.0Hz, 1H), 7.92 (t, J=6.6Hz, 1H), 7.96 (t, J=5.4Hz,
1H), 8.79 (d, J=6.6Hz, 1H), 8.84 (d, J=6.0Hz, 1H), 9.06 (d, J=7.2Hz, 1H), 9.85 (d, J=
7.8Hz,1H).In addition, secondary proof is carried out by mass spectrum, as a result as shown in figure 5, specially MS (ESI):M/z=325.0
[M-H]-.It can determine that synthesized product is title intermediate by analysis.
3) under nitrogen protective condition, by the dicarboxyl anthroic acid acid anhydrides (0.82g, 2.5mmol) of 6- bromo- 1,2 and n-butylamine
(986ul, 10mmol) is dissolved in ethanol (50~57.5ml) and stirred 10 minutes；Stirring is warming up to 79 DEG C, and back flow reaction 8 is small
When；Room temperature is cooled to, after rotary evaporation removes ethanol, is extracted with dichloromethane/deionized water, collects organic phase, dried, mistake
Filter, rotary evaporation remove solvent, gained solid by silica gel chromatography post purifying (dichloromethane), obtain the positive fourths of brown solid powder N-
The bromo- anthracene acid imides of base -6- (0.46g, yield 48%).The product is characterized by proton nmr spectra, as a result such as Fig. 6 institutes
Show, be specially：1H NMR(CDCl3,600MHz,ppm):1.00 (t, J=5.4Hz, 3H), 1.50 (m, 2H), 1.77 (m, 2H),
4.26 (t, J=6.0Hz, 2H), 7.73 (t, J=7.2Hz, 1H), 7.79-7.85 (m, 2H), 8.70 (d, J=6.0Hz, 1H),
8.79 (d, J=6.6Hz, 1H), 8.91 (d, J=7.2Hz, 1H), 10.07 (d, J=7.2Hz, 1H).In addition, entered by mass spectrum
Secondary proof is gone, as a result as shown in fig. 7, being specially：MS(ESI):M/z=380.7 [M]-.It can determine to be closed by analysis
Into product be title intermediate.
4) under nitrogen protective condition, by the bromo- anthracene acid imides (0.46g, 1.2mmol) of N- normal-butyls -6-, sodium methoxide
(0.44g, 8mmol) is dissolved in methanol (12~27.6ml) with cupric sulfate pentahydrate (8.4~14mg, 0.036~0.06mmol) to be stirred
Mix 10 minutes；70 DEG C are gradually heating to, is stirred at reflux reaction 8-12 hours；Room temperature is cooled to, after rotary evaporation removes methanol, is used
Dichloromethane/deionized water extraction, collects organic phase, dries, filtering, rotary evaporation removes solvent, and gained solid is through layer of silica gel
Analyse post purifying (dichloromethane：Methanol=10：1) yellow solid powder N- normal-butyls -6- methoxyl groups-anthracene acid imide, is obtained
(0.34g, yield 85%).The product is characterized by proton nmr spectra, as a result as shown in figure 8, being specially：1H NMR
(CDCl3,600MHz,ppm):1.01 (t, J=6.0Hz, 3H), 1.50 (m, 2H), 1.78 (m, 2H), 4.23 (s, 3H), 4.28
(t, J=6.6Hz, 2H), 7.66 (t, J=6.6Hz, 1H), 7.74 (t, J=6.6Hz, 1H), 7.84 (t, J=7.2Hz, 1H),
8.46 (d, J=6.6Hz, 1H), 8.65 (d, J=6.6Hz, 1H), 8.77 (d, J=6.0Hz, 1H), 10.08 (d, J=6.0Hz,
1H) by mass spectrum in addition, carried out secondary proof, as a result as shown in figure 9, being specially：MS(ESI):M/z=333.0 [M]-
It can determine that synthesized product is title intermediate by analysis.
5) under nitrogen protective condition, N- normal-butyls -6- methoxyl groups-anthracene acid imide (0.34g, 1.0mmol) adds
In 10ml hydroiodic acid (content 57%), 132 DEG C of back flow reaction 8-12 hours are heated to；Room temperature is cooled to, with 2M hydroxide
The mixed solution of reaction is adjusted to faintly acid by sodium solution, is filtered and is repeatedly washed, through silica gel column chromatography after gained solid is spin-dried for
Purify (dichloromethane：Methanol=7：1) red solid powder N- normal-butyls -6- hydroxyls-anthracene acid imide (0.16g, yield, is obtained
52%).The product is characterized by proton nmr spectra, as a result as shown in Figure 10, is specially：1HNMR(CDCl3,
600MHz,ppm):1.02 (t, J=5.4Hz, 3H), 1.51 (m, 2H), 1.79 (m, 2H), 4.23 (t, J=6.6Hz, 2H),
7.66 (t, J=6.6Hz, 1H), 7.70-7.78 (m, 2H), 8.57 (d, J=6.6Hz, 1H), 8.71 (d, J=6.0Hz, 1H),
8.79 (d, J=6.6Hz, 1H), 9.98 (d, J=6.0Hz, 1H).The product is characterized by carbon-13 nmr spectra, passed through
Proton nmr spectra characterizes to the product, as a result as shown in figure 11, is specially：13C NMR(CD3OD,600MHz,ppm):
14.01,20.52,30.1,39.66,114.85,120.25,122.86,125.67,126.78,129.21,130.75,
153.86,162.65,167.18.In addition, having carried out secondary proof by mass spectrum, as a result as shown in figure 12, it is specially：MS
(ESI):M/z=317.1 [M-H]-can determine that synthesized product is target product by analysis.
The photostability of the fluorescence probe of 2 embodiment of embodiment 1
In 15W 365nm and 254nm ultraviolet light prolonged exposure 10 hours, N- normal-butyls -6- hydroxyls-anthracene imide fluorescent
Red fluorescence intensity of the probe in 522nm reduces 0.5%, it is indicated above that the fluorescent probe molecule has light good enough steady
It is qualitative, the light irradiation of long period can be subjected to.
Fluorescence of the embodiment 3N- normal-butyls -6- hydroxyls-anthracene imide fluorescent probe to isocyanate content in liquid environment
Detection
With N- normal-butyls -6- hydroxyls-anthracene imide fluorescent probe (prepared by embodiment 1) to isocyanates in methanol solution
Content is tested and analyzed.Fluorescence probe is diluted to concentration as 4 μM during test, by adding different amounts of isocyanate solution,
Fluorescence probe of the present invention fluorescence intensity at the 560nm and at 596nm is recorded, calculates I560/I596, it is as shown in table 1 below.At 4 μM
The methanol solution of N- normal-butyls -6- hydroxyls-anthracene imide fluorescent probe add the not fluorescence spectrum after same amount isocyanates and become
(in Figure 14, the amount of isocyanate added by a to j is followed successively by 40 μM, 15 μM, 10 μM, 5 μM, 4 μM, 3 μ as shown in figure 14 for change
M, 2 μM, 1 μM, 0.5 μM, 0M), I560/I596The variation tendency of ratio is as shown in figure 15.It is seen from figure 14 that in the absence of different
In the case of cyanate, N- normal-butyls -6- hydroxyls-anthracene imide fluorescent probe 522nm excite light irradiation under, in 596nm
Launch red fluorescence in left and right；And in the presence of isocyanates, fluorescence probe launches 560nm or so orange fluorescence, with
The content of isocyanates, which increases, causes red fluorescence to weaken, orange fluorescence enhancing.With orange fluorescence and the ratio of red fluorescence
Value can be used as detection signal, therefore can realize the Ratio-type fluoroscopic examination to isocyanates.
Stable Intramolecular electron transfer can occur for N- normal-butyls -6- hydroxyls-anthracene imide fluorescent probe, in N- positions
Supplied for electronic amino can shift electronics to the electrophilic hydroxyl on 6- positions so that the fluorescence probe in methanol solution
Launch 590nm feux rouges under 522nm exciting light.And when recognition group phenolic hydroxyl group and NCO generation esterification are anti-
Strain as after ester group, the electron-withdrawing power of group strengthens on 6- positions, cause the launch wavelength blue shift of fluorescence molecule.The positive fourths of N-
For base -6- hydroxyls-anthracene imide fluorescent probe after being acted on isocyanates, the principle of its change in fluorescence is as shown in figure 13.
Table 1
Embodiment 4
The present invention is used for a kind of embodiment for detecting the preparation method of the Test paper of isocyanate ester compound, this implementation
The preparation method of the example Test paper for being used to detect isocyanate ester compound is：By the fluorescence probe of 1mg embodiments 1
(N- normal-butyls -6- hydroxyls-anthracene acid imide) is dissolved in 1mL methanol or ethanol, and then with 100uL, the probe solution uniformly carries
It is rear stand-by on the clean filter paper cut, air-drying.
N- normal-butyls-6- the hydroxyls of embodiment 5-anthracene imide fluorescent probe in air ambient isocyanate content it is glimmering
Light detects
Fluorescence detection test made from embodiment 4 is positioned in the environment to be measured containing isocyanates after 5 minutes, used
Hand-held ultraviolet lamp 365nm wavelength light irradiations, test paper color change is observed, its color change is as shown in figure 16, Tu16Zhong, with
Time lengthening, test paper color is changed into light yellow from red.Test paper is respectively in acetone, toluene, chloroform, ether, acetic acid second
Detected in ester, propylene and formaldehyde air ambient, as a result to other materials in the complex environment of surface to the equal nothing of probe test paper
Influence, as shown in figure 17.In Figure 17, except the test paper being placed in the air ambient of chloroethyl isocyanate containing 2- show it is light yellow, its
The color of his test paper does not change, is still red, and it is selective and special thus to demonstrate Test paper made from embodiment 4
Property it is good, and stability is high.By the Test paper respectively in 2,4-TDI (2,4- toluene-2,4-diisocyanate), 2,6-TDI (2,6- bis-
Toluene isocyanate), MDI (methyl diphenylene diisocyanate), HDI (hexamethylene diisocyanate) and IPDI (different Fo Er
Ketone diisocyanate) detected in environment, viewing test result is as shown in figure 18 under 365nm uviol lamps, and test paper color is equal
Change, it is faint yellow that identical is presented.Test result indicates that Test paper is to different types of different made from embodiment 4
Cyanate has identical sensitiveness.
Embodiment 6
The present embodiment has investigated the N- normal-butyls -6- hydroxyls-anthracene imide fluorescent probe in detecting isocyanic acid of the invention prepared
The sensitivity of ester.The specific method of investigation is：Not same amount is added into N- normal-butyls -6- hydroxyls-anthracene acid imide that concentration is 4 μM
Isocyanates (R-NCO), using isocyanates (R-NCO) concentration as abscissa, fluorescence probe excitation wavelength be 522nm, it is anti-
Ratio I between seasonable under the conditions of 30s at 560nm with fluorescence intensity at 596nm560/I596For ordinate, calibration curve is drawn.It is different
Regression curve of the cyanate (R-NCO) in low strength range is as shown in figure 19, and its regression curve side is：Y=0.0687+K × x
(R=0.998)；Wherein, y is the ratio I of fluorescence probe fluorescence intensity at 560nm and at 596nm560/I596, x is isocyanic acid
Ester concentration [R-NCO], K=0.2152.
Test limit LOD=3 × S.D./K, wherein K are the slopes of curvilinear equation, and S.D. represents does not have probe in R-NCO
Fluorescence intensity ratio standard deviation.
LOD=3 × 0.0069/0.2152nmol/L=96nmol/L, from the result, fluorescence probe detection of the present invention
The sensitivity of isocyanate ester compound is higher.
As fully visible：N- normal-butyls -6- hydroxyls-anthracene imide fluorescent probe prepared by the present invention can be used for liquid environment
In detection and analysis with isocyanates in chemical example in air ambient.Sample is diluted with methanol solution liquid, and adds this hair
The probe dispersion liquid of bright middle preparation, qualitative and quantitative detection analysis can be carried out to sample.
Fluorescence probe N- normal-butyls -6- hydroxyls-anthracene acid imide is dissolved in methanol or ethanol by the present invention, then will be contained
The solution of fluorescence probe is uniformly loaded in the fluorescence detection test that detection isocyanate content is made on the clean filter paper cut.
The detection method of isocyanates in rapidly and efficiently easy air is established, the detection method only needs to survey at ambient temperature
Paper of having a try is placed in air 5 minutes, and then irradiating observation test paper color change with 365nm using hand-held ultraviolet lamp can draw
The substantially concentration of isocyanates in air, and other materials are not influenceed test paper in by complicated air ambient.To isocyanates
The detection of class compound has specific aim.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Understand, technical scheme can be modified or equivalent substitution, without departing from the essence of technical solution of the present invention
And scope.
Claims (10)
- A kind of 1. fluorescence probe, it is characterised in that：The fluorescence probe has the structural formula as shown in formula (I)：
- A kind of 2. preparation method of fluorescence probe as claimed in claim 1, it is characterised in that：Comprise the following steps：(1) using 9- bromines anthracene and oxalyl chloride as raw material, 6- bromine aceanthrene of the acylation reaction preparation structure formula as shown in formula (∏) is passed through Alkene -1,2- diketone；(2) 6- bromines aceanthrylene -1,2- diketone made from potassium hydrogen persulfate oxidation step (1), preparation structure formula such as formula (III) are used The bromo- 1,2 dicarboxyl anthroic acid acid anhydrides of shown 6-；(3) with the dicarboxyl anthroic acid acid anhydrides of 6- made from step (2) bromo- 1,2 and n-butylamine for raw material, preparation structure formula such as formula (IV) institute The bromo- anthracene acid imides of N- normal-butyls -6- shown；(4) using the bromo- anthracene acid imides of N- normal-butyls -6- made from step (3) and sodium methoxide as raw material preparation structure formula such as formula (V) Shown N- normal-butyls -6- methoxyl groups-anthracene acid imide；(5) with N- normal-butyls -6- methoxyl groups-anthracene acid imide made from step (4) and acid for raw material, preparation structure formula such as formula (I) Shown fluorescence probe；
- 3. the preparation method of fluorescence probe as claimed in claim 2, it is characterised in that：Comprise the following steps：(1) 9- bromines anthracene, oxalyl chloride solution, alchlor and carbon disulfide are mixed, under nitrogen or inert gas shielding, in 0 DEG C After being reacted in ice bath, 8-10 hours are reacted under room temperature condition；Then hydrochloric acid is added, in 50 DEG C of reactions；It is finally cooled to room Temperature, filtering, dry, purified filter solid, obtain 6- bromine aceanthrylene -1,2- diketone；(2) 6- bromine aceanthrylene -1,2- diketone and potassium hydrogen persulfate are dissolved in methanol, entered under nitrogen or inert gas shielding Row reaction；Then reaction product is spin-dried for, is filtered after washing, the solid of purifying filtering gained, obtains the dicarboxyl anthroic acids of 6- bromo- 1,2 Acid anhydride；(3) the dicarboxyl anthroic acid acid anhydrides of 6- bromo- 1,2 and n-butylamine are dissolved in ethanol, carried out under nitrogen or inert gas shielding Reaction；Ethanol is removed after reaction, the product after ethanol is removed with dichloromethane and water extraction, collects organic phase；Re-dry, filtering Organic phase, the obtained rotated evaporation of solvent of filtrate, solid obtained by purifying rotary evaporation, obtain the bromo- anthracenes of N- normal-butyls -6- Acid imide；(4) N- normal-butyls -6- bromo- anthracene acid imide, sodium methoxide and mantoquita are dissolved in methanol, in nitrogen or inert gas shielding Under reacted；Methanol is removed after reaction, the product after methanol is removed with dichloromethane and water extraction, collects organic phase；Do again It is dry, filtering organic phase, the obtained rotated evaporation of solvent of filtrate, purifying rotary evaporation obtained by solid, obtain N- normal-butyls- 6- methoxyl groups-anthracene acid imide；(5) hydroiodic acid is added into N- normal-butyls -6- methoxyl groups-anthracene acid imide, after reaction, adjusts the pH value of reaction product, then Filtering, purifying filtering gained solid, obtains fluorescence probe of the structural formula as shown in formula (I).
- 4. the preparation method of fluorescence probe as claimed in claim 3, it is characterised in that：In step (1)~(5), adopt Purified with silica gel column chromatography.
- 5. the preparation method of fluorescence probe as claimed in claim 3, it is characterised in that：In the step (1), according to every mmoles Your 9- bromines anthracene adds the ratio of 4~5mL carbon disulfide, and 9- bromine anthracenes are added in carbon disulfide；In the step (2), according to every MM 6- bromine aceanthrylenes -1,2- diketone adds the ratio of 10~23mL methanol, and 6- bromine aceanthrylene -1,2- diketone is added into methanol In；In the step (3), the ratio of 10~23mL ethanol is added according to the dicarboxyl anthroic acid acid anhydrides of every mM of 6- bromo- 1,2, by 6- Bromo- 1,2 dicarboxyl anthroic acid acid anhydride is added in ethanol；In the step (4), according to every mM of bromo- anthracene acid imide of N- normal-butyls -6- The ratio of 10~23mL methanol is added, the bromo- anthracene acid imides of N- normal-butyls -6- are added in methanol, and the N- normal-butyls -6- The mol ratio of bromo- anthracene acid imide and mantoquita is 1：0.03~0.05.
- 6. application of the fluorescence probe as claimed in claim 1 in isocyanate ester compound is detected.
- 7. fluorescence probe as claimed in claim 1 is preparing kit or Test paper for detecting isocyanate ester compound In application.
- A kind of 8. kit or Test paper for being used to detect isocyanate ester compound, it is characterised in that：The kit or Test paper contains fluorescence probe as claimed in claim 1.
- A kind of 9. preparation method for being used to detect the Test paper of isocyanate ester compound, it is characterised in that：Including following step Suddenly：(1) fluorescence probe as claimed in claim 1 is dissolved in alcohol, obtains the solution containing the fluorescence probe；(2) step (1) resulting solution is applied on filter paper or filter paper is dipped into step (1) resulting solution, then filter paper is dried in the air It is dry, obtain the Test paper for detecting isocyanate ester compound.
- 10. the preparation method as claimed in claim 9 for being used to detect the Test paper of isocyanate ester compound, its feature exist In：The alcohol is methanol or ethanol.
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| CN109970711A (en) * | 2019-04-26 | 2019-07-05 | 武汉华星光电半导体显示技术有限公司 | Red hot activation delayed fluorescence material and preparation method thereof, electroluminescent device |
| CN110016336A (en) * | 2019-05-14 | 2019-07-16 | 天津理工大学 | A kind of fluorescence probe and its preparation method and application for detecting content of nitrite |
| CN110286105A (en) * | 2019-03-08 | 2019-09-27 | 华南农业大学 | A kind of fluorescence probe and preparation method thereof |
| CN110330444A (en) * | 2019-06-29 | 2019-10-15 | 华南理工大学 | A kind of fluorescent chemicals and preparation method and its application as test paper type detection probe for the detection of isocyanates substance |
| CN110407748A (en) * | 2019-07-05 | 2019-11-05 | 湖北工程学院 | A kind of 1,9- anthracene imide compound being connected with o-phenylenediamine and preparation method thereof and purposes |
| CN111548307A (en) * | 2020-04-10 | 2020-08-18 | 华南农业大学 | Fluorescent probe for detecting cutinase on surface of plant leaf and preparation method thereof |
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| CN110286105B (en) * | 2019-03-08 | 2021-10-19 | 华南农业大学 | Fluorescent probe and preparation method thereof |
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| WO2020215439A1 (en) * | 2019-04-26 | 2020-10-29 | 武汉华星光电半导体显示技术有限公司 | Red thermally activated delayed fluorescent material and preparation method therefor, and electroluminescent device |
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| CN110330444B (en) * | 2019-06-29 | 2021-05-14 | 华南理工大学 | Fluorescent compound for detecting isocyanate substances, preparation method and application of fluorescent compound as test paper type detection probe |
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