CN104031108A - Fluorescent compound and preparation method thereof, as well as method for preparing sensing film by using fluorescent compound and application thereof - Google Patents
Fluorescent compound and preparation method thereof, as well as method for preparing sensing film by using fluorescent compound and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorescent compound and a preparation method thereof, as well as a method for preparing a sensing film by using the fluorescent compound and an application thereof. Cholesterol and a sugar structure are simultaneously introduced into oligonucleotides polystyrene acetylene, and the synthetic fluorescent compound has more abundant assembly behavior due to hydrophobicity of the cholesterol and hydrophily of the sugar structure. The sensing film prepared by the compound has a uniform and controllable microstructure, has good stability, long service life and high identification sensitivity on hydrogen chloride steam. The sensitive detection on the hydrogen chloride steam can be achieved by combined utilization of the film and a commodity fluorescence instrument. In addition, a special detector for hydrogen chloride steam also can be developed by instrumentation of the sensing film.
Description
Technical field
The invention belongs to fluorescent chemicals preparing technical field, be specifically related to a kind of fluorescent chemicals and preparation method thereof and prepare the methods and applications of sense film with utilizing this fluorescent chemicals.
Background technology
Along with increasingly sharpening of global environmental pollution and ecological degradation, environmental problem more and more becomes the important factor that is related to mankind's life quality, thereby the detection of atmospheric polluting material has been caused to domestic and international scientist's extensive concern.Hydrogen chloride gas, as common are harmful gas, has strong impulse effect to eye and respiratory mucosa, and long-term higher concentration contact, can cause chronic bronchitis, gastrointestinal dysfunction and tooth erosion disease etc.; In addition, plant also has certain tolerance limit to hydrogen cloride concentration, once exceed this threshold concentration, the cell of plant and histoorgan will come to harm, and physiological function is obstructed with growing, and finally causes death; Meanwhile, in atmosphere, hydrogen cloride concentration is too high, also can cause acid rain, thereby causes the corrosion of soil acidification and buildings.
Masanobu Matsuguchi group adopts the method for atom transfer radical polymerization to prepare PNIPAM nanoparticle, and be coated on quartz resonator, successfully realize the sensitive reversible detection to 1ppm hydrogen chloride gas by QCM (Quartz Crystal Microbalance) technology; Aniline and formaldehyde copolymerization are obtained nano composite material by Prafull group, and adulterate and prepare the film that utilizes electrochemical signals to detect hydrogen chloride gas with iron and aluminium; Myung Hwa Kim seminar introduces Trimethylamine in poly-diacetylene, and resulting polymers and polyvinyl alcohol doping are prepared to electrostatic spinning, and first passage material fluorescence color changes the visual detection having realized hydrogen chloride gas.Although these methods have realized the Sensitive Detection to hydrogen chloride gas to a certain extent, also Shortcomings part, such as: the time of response is long, and selectivity is low, is difficult to device etc.Fluorescence membrane due to its high sensitivity, selectivity and simple to operate, instrument is required to the advantages such as lower, by more and more for sensor research.Prior art discloses the side chain of cholesterol being introduced to conjugation fluorescence molecule, and by this molecule and diamines polymerization, obtains having the polymkeric substance containing cholesterol of fluorescence property, has effectively realized the highly sensitive detection to hydrogen chloride gas.But this film assembling poor performance, and can not reuse, this has just hindered its practical application greatly.
Summary of the invention
The object of the present invention is to provide a kind of fluorescent chemicals and preparation method thereof to prepare the method for sense film with utilizing this fluorescent chemicals, this fluorescent chemicals possesses the advantage such as supramolecule characteristic and easy assembling, thereby the sense film of being prepared by this fluorescent chemicals can be realized the Sensitive Detection to hydrogenchloride steam.
The present invention is achieved through the following technical solutions:
A kind of fluorescent chemicals, the structural formula of this fluorescent chemicals is as follows:
Wherein, m=0,1 or 2, n=5,8,10 or 12.
A preparation method for fluorescent chemicals, comprises the following steps:
1), under nitrogen protection, sugared pentaacetate and acetic acid hydrazine are dissolved in DMF, at 50～60 DEG C, stir 2～4 hours, in the reaction solution obtaining, add ethyl acetate after washing, collect organic phase, except desolventizing obtains colorless oil, i.e. compound 1;
2), under argon shield, compound 1, Trichloroacetonitrile and cesium carbonate are dissolved in anhydrous methylene chloride in 0 DEG C, 0 DEG C of insulation reaction 1～3 hour, the solid filtering that reaction is produced, filtrate is condensed into oily matter, and oily matter is carried out to column chromatography separation, obtains compound 2;
3) under argon shield, compound 5 and amino ethoxy ethanol substituent are dissolved in methylene dichloride, stir 16～20 hours at 40～50 DEG C; naturally cool to room temperature, add sodium borohydride, stirring at normal temperature reaction 1～2 hour; reaction finishes after washing; use again dichloromethane extraction, collect organic phase, then organic phase is dried and is filtered; filtrate is except desolventizing and carry out column chromatography separation; obtain yellow-green colour solid 6, wherein, the structural formula of described compound 5 is:
The structural formula of described amino ethoxy ethanol substituent is:
4) under argon shield, yellow-green colour solid 6 and compound 2 are dissolved in anhydrous methylene chloride, add trimethylsilyl trifluoromethanesulfonic acid fat, ice bath stirred after 2～4 hours, washed with the sodium bicarbonate aqueous solution that mass concentration is 5%, used dichloromethane extraction, collect organic phase, then organic phase is dried and is filtered, filtrate, except the laggard row column chromatography of desolventizing separates, obtains flaxen compound 7;
5) under argon shield; compound 7 is dissolved in the mixed solvent of methyl alcohol and tetrahydrofuran (THF); drip sodium methoxide solution; under room temperature, stir 4～6 hours; it is neutral adding acidic cation-exchange resin to reaction solution, obtains mixed solution, this mixed solution is removed to the laggard row column chromatography of desolventizing and separate; obtain yellow-green colour solid, i.e. fluorescent chemicals.
Step 1) in, the mol ratio of sugared pentaacetate, acetic acid hydrazine and DMF is 1:(1～1.3).
Described sugared pentaacetate is β-D alpha-glucose pentaacetate, α-D alpha-glucose pentaacetate, β-D semi-lactosi pentaacetate, β-L semi-lactosi pentaacetate or α-D seminose pentaacetate.
Step 2) in, the mol ratio of compound 1, Trichloroacetonitrile and cesium carbonate is 1:(2～4): (0.2～0.4); Step 2) described column chromatography separates and adopts the volume ratio of ethyl acetate: sherwood oil=1:1 to mix the eluent making to separate.
Step 3) in, the mol ratio of compound 5, amino ethoxy ethanol substituent and sodium borohydride is 1:(2.5～4): (3～5); Step 3) described column chromatography separates and adopts the volume ratio of methylene dichloride: methyl alcohol=10:1 to mix the eluent making to separate.
Step 4) in, the mol ratio of compound 6, compound 2 and trimethylsilyl trifluoromethanesulfonic acid fat is 1:(2～4): (0.1～0.3); Step 4) described column chromatography separates and adopts the volume ratio of methylene dichloride: methyl alcohol=15:1 to mix the eluent making to separate.
Step 5) in, in compound 7, sodium methoxide solution, the mol ratio of sodium methylate, methyl alcohol and tetrahydrofuran (THF) is 1:(0.8～1.6): (500～600): (100～150); Step 5) described column chromatography separates and adopts the volume ratio of methylene dichloride: methyl alcohol=4:1 to mix the eluent making to separate.
Adopt fluorescent chemicals to prepare a method for fluorescence sense film, comprise the following steps:
1) fluorescent chemicals is dissolved in trichloromethane, makes the storing solution that concentration is 0.18mg/mL～1.80mg/mL;
2) under the atmosphere that is 60%～75% in relative humidity, the storing solution that is 0.18mg/mL～1.80mg/mL by concentration is coated in clean glass matrix surface uniformly, leaves standstill 20～60min, makes fluorescence sense film.
A kind of fluorescence sense film is in the application of preparing in fluorescence sense device.
Compared with prior art, the present invention has following useful technique effect:
The synthetic method of fluorescent chemicals of the present invention has been introduced oligomerization phenylacetylene by cholesterol and sugared structure simultaneously.Wherein cholesterol has the advantages such as rigid-skeleton, multichiral center and strong Van der Waals accumulation; Sugar structure has multiple hydrogen bonded site and good biocompatibility.Fluorescent chemicals prepared in the present invention is introduced cholesterol and sugared structure in oligomerization phenylacetylene simultaneously, this has just not only given target compound above-mentioned all supramolecule characteristics, more because the hydrophobicity of cholesterol and the wetting ability of sugared structure make this compound have the more assembly behavior of horn of plenty.The fluorescence sense film preparing with this compound, has evenly controlled microtexture, and good stability, long service life, highly sensitive to the identification of hydrogen chloride vapors, what is more important, detect completely reversibility, this has just laid solid foundation for it for the preparation of fluorescence sense device.This class film is combined to use with commodity fluorescent instrument and can realize the Sensitive Detection to environment hydrogen chloride gas, in addition, by sense film device, also can develop hydrogen chloride gas special detector.
Brief description of the drawings
Fig. 1 is the excitation-emission spectrogram of the fluorescence sense film that makes of the present invention;
Fig. 2 is the micro-structure diagram of fluorescence sense film;
Fig. 3 is the fluorescence sense figure of fluorescence sense film in different concns hydrogen chloride gas;
Fig. 4 is the recovery of fluorescence sense film to hydrogen chloride gas;
Fig. 5 is that different sour gas and common solvent vapour are to film Quenching of fluorescence efficiency diagram;
Fig. 6 is the mass spectrum of the fluorescent chemicals that makes of the embodiment of the present invention 1.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
The preparation method of fluorescent chemicals of the present invention, comprises the following steps:
1, prepare compound 5 (Chinese invention patent that is specifically CN102604140A referring to publication number)
1. synthetic iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(methoxyl group)-benzene
Under nitrogen protection, to the mixture that adds respectively iodine, Potassium Iodate and water and the vitriol oil in the acetum of anisole; 80 DEG C of reactions 8～12 hours, suction filtration, vacuum-drying, obtains white solid, and 2, iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(methoxyl group)-benzene.Wherein, be 1:(0.8～1.2 to the mol ratio of anisole, iodine, Potassium Iodate, water and the vitriol oil): (0.2～0.6): (150～190): (1～3).Its reaction equation is as follows:
2. synthetic iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene
Under nitrogen protection, iodo-2,5-bis-Isosorbide-5-Nitrae-bis-(methoxyl group)-benzene is dissolved in to methylene dichloride, and under-78 DEG C of conditions, in solution, drips boron tribromide; Reaction is stirred 14～18 hours, suction filtration, and vacuum-drying, obtains white solid, and 2, iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(hydroxyl)-benzene.Wherein, the mol ratio of iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(methoxyl group)-benzene, boron tribromide and methylene dichloride is 1:(2～4): (30～50).Its reaction equation is as follows:
3. synthetic compound 3
Under argon shield; cholesterol, dibromo substituted straight chain alkane and potassium hydroxide are dissolved in anhydrous tetrahydro furan; at 80 DEG C, react 14～18 hours; rotary evaporation is except desolventizing; be washed to neutrality; recrystallizing methanol, finally uses methylene dichloride: sherwood oil=1:1 to carry out column chromatography separation, obtains white solid.Wherein the mol ratio of cholesterol, dibromo substituted straight chain alkane, potassium hydroxide and tetrahydrofuran (THF) is 1:(4～6): (3～7): (30～50).Reaction equation is:
In formula, the value of n is 5 or 8 or 10 or 12.
4. synthetic compound 4
Under argon shield, by compound 3,2, iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(hydroxyl)-benzene, salt of wormwood are dissolved in anhydrous DMF, react 14～18 hours at 160 DEG C.Reaction finishes, and solution is poured in large water gaging and separated out precipitation, suction filtration, vacuum-drying, carries out column chromatography separation with methylene dichloride: sherwood oil=3:2, obtains white solid.Wherein, the mol ratio of iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene, compound 3, salt of wormwood and DMF is 1:(2～4): (20～30): (150～180).Reaction equation is:
5. synthetic compound 5
Under argon shield, by compound 4, alkynyl phenyl aldehyde, cuprous iodide, tetraphenylphosphonium palladium are dissolved in anhydrous Diisopropylamine and dry toluene, react 10～14 hours at 70 DEG C.After reaction finishes, be cooled to room temperature, washing dichloromethane extraction, collects organic phase, and rotary evaporation is to remove solvent.Gained brown oil obtains yellow solid by recrystallizing methanol, carries out column chromatography separation with methylene dichloride: methyl alcohol=100:1, obtains yellow-green colour solid, i.e. compound 5.Wherein, compound 4, to the mol ratio of alkynyl phenyl aldehyde, cuprous iodide, tetraphenylphosphonium palladium, Diisopropylamine and toluene be: 1:(2～4): (0.04～0.06): (0.04～0.06): (40～60): (60～80).Reaction equation is:
Preferably, the step of synthetic iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(methoxyl group)-benzene 1. in, be 1:0.4:1:170:2 to the mol ratio of anisole and Potassium Iodate, iodine, Glacial acetic acid, sulfuric acid;
Preferably, the step of synthetic iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene 2. in, the mol ratio of iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(methoxyl group)-benzene and boron tribromide, methylene dichloride is 1:3:40;
Preferably, synthetic compound 3 steps 3. in, the mol ratio of cholesterol and potassium hydroxide, dibromo substituted straight chain alkane, tetrahydrofuran (THF) is 1:5:5:40;
Preferably, synthetic compound 4 steps 4. in, the mol ratio of iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene and compound 3, salt of wormwood, DMF is 1:3:25:170;
Preferably, synthetic compound 5 steps 5. in, compound 4 be 1:3:0.05:0.05:50:70 to the mol ratio of acetylenylbenzene formaldehyde, tetraphenylphosphonium palladium, cuprous iodide, Diisopropylamine, toluene;
2, prepare fluorescent chemicals
6. synthetic compound 1
Under nitrogen protection, sugared pentaacetate and acetic acid hydrazine are dissolved in DMF, in 55 DEG C of reactions 2～4 hours.Reaction finishes, and in reaction solution, adds ethyl acetate, by massive laundering, collects organic phase, except desolventizing obtains colorless oil.Wherein, the mol ratio of sugared pentaacetate, acetic acid hydrazine and DMF is 1:(1～1.3): (50～70), reaction equation is as follows:
7. synthetic compound 2
Under argon shield, compound 1, Trichloroacetonitrile and cesium carbonate are dissolved in anhydrous methylene chloride in 0 DEG C.Ice bath stirs 1～3 hour, the solid filtering that reaction is produced, and filtrate rotary evaporation, gained oily matter is crossed post taking ethyl acetate: sherwood oil=1:1 as developping agent, obtains faint yellow oily matter.Wherein the mol ratio of compound 1, Trichloroacetonitrile, cesium carbonate and methylene dichloride is 1:(2～4): (0.2～0.4): (40～70), reaction equation is as follows:
8. synthetic compound 6
Under argon shield, compound 5 and amino ethoxy ethanol substituent are dissolved in methylene dichloride, 45 DEG C are reacted 16～20 hours.Naturally cool to room temperature, add sodium borohydride, stirring at normal temperature 1 hour, rotary evaporation, with except desolventizing, is washed dichloromethane extraction, collects organic phase, anhydrous MgSO
4dry, filter, by filtrate rotary evaporation, gained solid methylene dichloride: methyl alcohol=10:1 carries out column chromatography separation as developping agent, obtains yellow-green colour solid.Wherein, the mol ratio of compound 5, amino ethoxy ethanol substituent, sodium borohydride and methylene dichloride is 1:(2.5～4): (3～5): (140～180).Reaction equation is:
Wherein the value of m is 0 or 1 or 2, n=5,8,10 or 12.
9. synthetic compound 7
Under argon shield, compound 6 and compound 2 are dissolved in anhydrous methylene chloride, carefully add trimethylsilyl trifluoromethanesulfonic acid fat, ice bath stirs 2～4 hours.Reaction finishes, and washes with 5% sodium bicarbonate aqueous solution, and dichloromethane extraction, collects organic phase, anhydrous MgSO
4dry, filter, by filtrate rotary evaporation, gained solid methylene dichloride: methyl alcohol=15:1 crosses post, obtains faint yellow solid, i.e. compound 7.Wherein, the mol ratio of compound 6, compound 2, trimethylsilyl trifluoromethanesulfonic acid fat and methylene dichloride is 1:(2～4): (0.1～0.3): (130～150).Reaction equation is:
10. synthetic fluorescent chemicals
Under argon shield, compound 7 is dissolved in the mixed solvent of methyl alcohol and tetrahydrofuran (THF), drips sodium methoxide solution, the concentration of sodium methoxide solution is 0.2mmol/mL; Stirring at room temperature 4～6 hours, adding acidic cation-exchange resin is neutrality to reaction solution, by mixed solution rotary evaporation, gained solid methylene dichloride: methyl alcohol=4:1 is that developping agent is crossed post, obtains yellow-green colour solid, i.e. target product fluorescent chemicals.Wherein, the mol ratio of compound 7, sodium methylate, methyl alcohol, tetrahydrofuran (THF) is 1:(0.8～1.6): (500～600): (100～150).Reaction equation is:
Preferably, the step of synthetic compound 1 6. in, the mol ratio of sugared pentaacetate, acetic acid hydrazine and DMF is 1:1.1:60;
Preferably, the step of synthetic compound 2 7. in, the mol ratio of compound 1, Trichloroacetonitrile, cesium carbonate and methylene dichloride is 1:3:0.3:50;
Preferably, synthetic compound 6 steps 8. in, the mol ratio of compound 5,2-(2-amino ethoxy) ethanol, sodium borohydride and methylene dichloride is 1:3:4:160;
Preferably, the step of synthetic compound 7 9. in, the mol ratio of compound 6, compound 2, trimethylsilyl trifluoromethanesulfonic acid fat and methylene dichloride is 1:3:0.2:140;
Preferably, the step of synthetic target product fluorescent chemicals 10. in, the mol ratio of compound 7, sodium methylate, methyl alcohol, tetrahydrofuran (THF) is 1:1.1:540:135.
3, prepare the method for fluorescence sense film
Fluorescent chemicals is dissolved in trichloromethane, is prepared into the storing solution of 0.18mg/mL～1.80mg/mL.Get 30～50 μ L storing solutions and under the atmosphere of relative humidity 60%～75%, be evenly coated in clean glass matrix surface, place and within 20～60 minutes, treat that its solvent evaporates is complete, sealing is preserved, and prepares fluorescence sense film.
Preferably, fluorescent chemicals is dissolved in trichloromethane, is prepared into the storing solution of 1.80mg/mL.Get 30 μ L storing solutions at every turn and under the atmosphere of relative humidity 75%, be evenly coated in clean glass matrix surface, place and within 20～60 minutes, treat that its solvent evaporates is complete, sealing is preserved, and prepares fluorescence sense film.
Embodiment 1
1, preparation is containing the fluorescent chemicals of cholesterol and sugared structure
1. synthetic iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(methoxyl group)-benzene
Under nitrogen protection, in 140mL acetum, add respectively the aqueous sulfuric acid 15mL of 2.0g to anisole, 4.0g iodine, 1.22g Potassium Iodate and massfraction 10%.80 DEG C are stirred 10 hours, and by a large amount of solid suction filtrations that produce, vacuum-drying, obtains white solid, and 2, iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(methoxyl group)-benzene.The wherein mol ratio 1:1:0.4:170:2 to anisole, iodine, Potassium Iodate, acetic acid and the vitriol oil;
2. synthetic iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene
Under nitrogen protection, by 7.8g2, iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(methoxyl group)-benzene is dissolved in 50mL methylene dichloride, and under-78 DEG C of conditions, in solution, drips 5.58mL boron tribromide.After being added dropwise to complete, stirring at room temperature 16 hours, by a large amount of solid suction filtrations that produce, vacuum-drying, obtains white solid, is iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene.Wherein, the mol ratio of iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(methoxyl group)-benzene, boron tribromide and methylene dichloride is 1:3:40;
3. synthetic compound 3
Under argon shield, by 6.0g cholesterol, 21.0g1,8-bis-bromooctanes and 4.4g potassium hydroxide are dissolved in 50mL anhydrous tetrahydro furan, stir 16 hours at 80 DEG C, and rotary evaporation is except desolventizing, washing dichloromethane extraction, rotary evaporation obtains yellow oil, and recrystallizing methanol is carried out column chromatography separation with methylene dichloride: sherwood oil=1:1, obtain white solid, be compound 3; Wherein, cholesterol, 1, the mol ratio of 8-bis-bromooctanes, potassium hydroxide and tetrahydrofuran (THF) is 1:5:5:40;
4. synthetic compound 4
Under argon shield, by 4.0g compound 3,0.85g2, iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(hydroxyl)-benzene, 8.0g salt of wormwood are dissolved in the anhydrous DMF of 30mL, stir 16 hours at 160 DEG C.Reaction finishes, and solution is poured into water, and has a large amount of Precipitations, suction filtration, and vacuum-drying, carries out column chromatography separation with methylene dichloride: sherwood oil=3:2, obtains white solid, i.e. compound 4; Wherein, the mol ratio of iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene, compound 3, salt of wormwood and DMF is 1:3:25:170;
5. synthetic compound 5
Under argon shield, 1.5g compound 4,0.43g are dissolved in the anhydrous Diisopropylamine of 7.8mL and 8.2mL dry toluene acetylenylbenzene formaldehyde, 0.01g cuprous iodide, 0.064g tetraphenylphosphonium palladium, stir 12 hours at 70 DEG C.After reaction finishes, be cooled to room temperature, washing dichloromethane extraction, by organic phase rotary evaporation, recrystallizing methanol, gained yellow solid methylene dichloride: methyl alcohol=100:1 carries out column chromatography separation, obtains yellow-green colour solid, is compound 5; Wherein compound 4, to the mol ratio of acetylenylbenzene formaldehyde, cuprous iodide, tetraphenylphosphonium palladium, Diisopropylamine and toluene be: 1:3:0.05:0.05:50:70;
6. synthetic compound 1
Under nitrogen protection, 4.0g β-D-Glucose pentaacetate and 0.99g acetic acid hydrazine are dissolved in 47mL DMF, stir 3 hours in 55 DEG C.Reaction finishes, and the extraction of washing ethyl acetate, collects organic phase, and rotary evaporation obtains colorless oil, is compound 1; Wherein, the mol ratio of β-D alpha-glucose pentaacetate, acetic acid hydrazine and DMF is 1:1.1:60;
7. synthetic compound 2
Under argon shield, 1.5g compound 1,1.85g Trichloroacetonitrile and 0.42g cesium carbonate are dissolved in 13.7mL anhydrous methylene chloride in 0 DEG C.Condition of ice bath stirs 3 hours, by solid filtering, and filtrate rotary evaporation, gained oily matter ethyl acetate: sherwood oil=1:1 is that developping agent is crossed post, obtains faint yellow oily matter, is compound 2; Wherein the mol ratio of compound 1, Trichloroacetonitrile, cesium carbonate and methylene dichloride is 1:3:0.3:50;
8. synthetic compound 6
Under argon shield, by 0.8g compound 5 and 0.186g2-(2-amino ethoxy) dissolve with ethanol, in 6mL methylene dichloride, 45 DEG C are stirred 10 hours.Naturally cool to room temperature, add 0.09g sodium borohydride, stirring at normal temperature 1 hour.Wash reaction solution with water dichloromethane extraction, collect organic phase, anhydrous MgSO
4dry, filter, filtrate rotary evaporation also carries out column chromatography separation with methylene dichloride: methyl alcohol=10:1 as developping agent, obtains yellow-green colour solid, is compound 6.Wherein, the mol ratio of compound 5,2-(2-amino ethoxy) ethanol, sodium borohydride and methylene dichloride is: 1:3:4:160;
9. synthetic compound 7
Under argon shield, 0.5g compound 6 and 0.5g compound 2 are dissolved in 3mL anhydrous methylene chloride, carefully add 0.014g trimethylsilyl trifluoromethanesulfonic acid fat, condition of ice bath stirs 3 hours.Reaction finishes, and washes with 5% sodium bicarbonate aqueous solution, and dichloromethane extraction, collects organic phase, anhydrous MgSO
4dry, filter, by filtrate rotary evaporation, gained solid methylene dichloride: methyl alcohol=15:1 crosses post, obtains faint yellow solid.Wherein, the mol ratio of compound 6, compound 2, trimethylsilyl trifluoromethanesulfonic acid fat and methylene dichloride is 1:3:0.2:140;
10. synthetic target product---fluorescent chemicals
Under argon shield; 0.2g compound 7 is dissolved in the mixed solvent of 2mL methyl alcohol and 1mL tetrahydrofuran (THF); add sodium methylate 0.0070g; stirring at room temperature 5 hours; adding acidic cation-exchange resin to reaction solution is neutrality; be also that developping agent is crossed post with methylene dichloride: methyl alcohol=4:1 by mixed solution rotary evaporation, obtain yellow-green colour solid, fluorescent chemicals.Wherein the mol ratio of compound 7, sodium methylate, methyl alcohol, tetrahydrofuran (THF) is 1:1.2:540:135.
The fusing point of the fluorescent chemicals making is: 93-95 DEG C.
Ir data is IR (KBr, cm
-1): 3438,2935,1052.
Mass spectrum MS (ESI, m/2z): calculated value: 931.6532, measured value: 931.6533.
Fig. 6 is the mass spectrogram of fluorescent chemicals, can be found out by the X-coordinate of spectrogram, actually records nuclear-cytoplasmic ratio and theoretical value is basically identical, illustrates and has obtained target product fluorescent chemicals.
2, prepare fluorescence sense film
Fluorescent chemicals is dissolved in trichloromethane, is prepared into the storing solution of 1.80mg/mL.Get 30 μ L storing solutions and under the atmosphere of relative humidity 75%, be evenly coated in clean glass matrix surface, place and within 30 minutes, treat that its solvent evaporates is complete, sealing is preserved, and prepares fluorescence sense film.
3, proof test:
The function fluorescent chemicals containing cholesterol, β-D glucose to synthesized in embodiment 1 is explored the detection of hydrogen chloride gas.
The excitation-emission spectrogram that accompanying drawing 1 is fluorescent chemicals, wherein a is excitation spectrum, b is emmission spectrum.As seen from the figure, maximum excitation wavelength is 375nm, and maximum emission wavelength is 494nm.
The assembling assumption diagram of the fluorescence sense film that accompanying drawing 2 makes for embodiment 1, (a) is the shows fluorescent microscopy images of film, is (b) its scanning electron microscope (SEM) photograph.As seen from the figure, by packaging assembly evenly and have compared with the ball-like structure of bigger serface and form, this just makes, and film and analysans are can contact area large, permeability is good, for its Sensitive Detection has been established solid foundation for film.
The fluorescence sense figure of the fluorescence sense film that accompanying drawing 3 makes for embodiment 1 to hydrogen chloride gas.Detect hydrogen cloride concentration used and be respectively 4.4ppb, 8.8ppb, 13.2ppb, 17.6ppb, 22.0ppb, 26.4ppb, 30.8ppb, 35.2ppb, 44.0ppb, 52.8ppb, 61.6ppb, 79.2ppb.In figure, curve a is blank, curve b is that chlorine hydride gas concentration is the fluorescent emission intensity curve of 4.4ppb, curve c is that chlorine hydride gas concentration is the fluorescent emission intensity curve of 8.8ppb, curve d is that chlorine hydride gas concentration is the fluorescent emission intensity curve of 13.2ppb, curve e is that chlorine hydride gas concentration is the fluorescent emission intensity curve of 17.6ppb, curve f is that chlorine hydride gas concentration is the fluorescent emission intensity curve of 22.0ppb, curve g is that chlorine hydride gas concentration is the fluorescent emission intensity curve of 26.4ppb, curve h is that chlorine hydride gas concentration is the fluorescent emission intensity curve of 30.8ppb, curve i is that chlorine hydride gas concentration is the fluorescent emission intensity curve of 52.8ppb.Show the increase along with hydrogen cloride concentration by figure, film fluorescence intensity is by significantly quencher.In the time that hydrogen chloride gas is 4.4ppb, film quenching of fluorescence degree just reaches 24%, and in the time that hydrogen cloride concentration reaches 52.8ppb, fluorescence intensity no longer reduces, and it is maximum that quencher degree reaches.
Accompanying drawing 4 is the recovery checking of fluorescence sense film to hydrogen chloride gas.Select respectively 44.0ppb, 88.0ppb, 880.0ppb, 15.4ppm, 154.0ppm, 616.0ppm, 1540.0ppm and saturated hydrogen chloride vapors to carry out quencher to film, then reply with saturated ammonia, result shows that film can recover initial fluorescence intensity, has good reversibility.
The quencher efficiency diagram of the fluorescence sense film that accompanying drawing 5 makes for embodiment 1 to steams such as hydrogenchloride and formic acid, acetic acid, methylene dichloride, tetrahydrofuran (THF)s, wherein hydrogen chloride gas used concentration is 66.0ppb, other gas concentration is 66.0ppm.As seen from the figure, this film can be realized the selectivity of hydrogen chloride vapors is detected.
Comprehensive above proof test can find out, the fluorescence sense film that the present invention makes possesses good fluorescence characteristic, has evenly controlled microtexture, hydrogen chloride vapors identified highly sensitive, and detects reversiblely, therefore, is highly suitable for preparing fluorescence sense device.
Embodiment 2
1. synthetic iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(methoxyl group)-benzene
Under nitrogen protection, in 140mL acetum, add respectively the aqueous sulfuric acid 15mL of 2.0g to anisole, 3.2g iodine, 1.22g Potassium Iodate and massfraction 10%, 80 DEG C are stirred 10 hours.By a large amount of solid suction filtrations that produce, vacuum-drying, obtains white solid.Be wherein 1:0.8:0.4:170:2 to the mol ratio of anisole, iodine, Potassium Iodate, acetic acid and the vitriol oil;
2. become iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene
Under nitrogen protection, by 7.8g2, iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(methoxyl group)-benzene is dissolved in 50mL methylene dichloride, and under-78 DEG C of conditions, in solution, drips 3.72mL boron tribromide.By a large amount of solid suction filtrations that produce, vacuum-drying, obtains white solid, is iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene.Wherein 2, the mol ratio of iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(methoxyl group)-benzene, boron tribromide and methylene dichloride is 1:2:40;
3. synthetic compound 3
Under argon shield, by 6.0g cholesterol, 12.6g1,8 two bromooctanes and 4.4g potassium hydroxide are dissolved in 50mL anhydrous tetrahydro furan, react 16 hours at 80 DEG C.Rotary evaporation is except desolventizing, washing dichloromethane extraction, and rotary evaporation obtains yellow oil, and recrystallizing methanol is carried out column chromatography separation with methylene dichloride: sherwood oil=1:1, obtains white solid.Wherein the mol ratio of cholesterol, 1,8 two bromooctane, potassium hydroxide and tetrahydrofuran (THF) is 1:3:5:40;
4. synthetic compound 4
Under argon shield, by 2.67g compound 3,0.85g2, iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(hydroxyl)-benzene, 8.0g salt of wormwood are dissolved in the anhydrous DMF of 30mL, react 16 hours at 160 DEG C.Reaction finishes, and solution is poured into water, and has a large amount of Precipitations, suction filtration, and vacuum-drying, carries out column chromatography separation with methylene dichloride: sherwood oil=3:2, obtains white solid.Wherein 2, the mol ratio of iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(hydroxyl)-benzene, compound 3, salt of wormwood and DMF is 1:2:25:170;
5. synthetic compound 5
Under argon shield, 1.5g compound 4,0.29g are dissolved in the anhydrous Diisopropylamine of 7.8mL and 8.2mL dry toluene alkynyl phenyl aldehyde, 0.01g cuprous iodide, 0.064g tetraphenylphosphonium palladium.At 70 DEG C, react 12 hours.After reaction finishes, be cooled to room temperature, washing dichloromethane extraction, by organic phase rotary evaporation, recrystallizing methanol, gained yellow solid methylene dichloride: methyl alcohol=100:1 carries out column chromatography separation, obtains yellow-green colour solid.Wherein compound 4, to the mol ratio of acetylenylbenzene formaldehyde, cuprous iodide, tetraphenylphosphonium palladium, Diisopropylamine and toluene be: 1:2:0.05:0.05:50:70;
6. synthetic compound 1
Under nitrogen protection, 4g β-D alpha-glucose pentaacetate and 0.9g acetic acid hydrazine are dissolved in to 47mLN, in dinethylformamide, in 55 DEG C of reactions 3 hours.Reaction finishes, and the extraction of washing ethyl acetate, collects organic phase, and rotary evaporation obtains colorless oil.Wherein the mol ratio of β-D alpha-glucose pentaacetate, acetic acid hydrazine and DMF is 1:1:60;
7. synthetic compound 2
Under argon shield, 1.5g compound 1,1.23g Trichloroacetonitrile and 0.42g cesium carbonate are dissolved in 13.7mL anhydrous methylene chloride in 0 DEG C.Ice bath stirs 3 hours, by solid filtering, and filtrate rotary evaporation, gained oily matter ethyl acetate: sherwood oil=1:1 is that developping agent is crossed post, obtains faint yellow oily matter.Wherein the mol ratio of compound 1, Trichloroacetonitrile, cesium carbonate and methylene dichloride is 1:2:0.3:50;
8. synthetic compound 6
Under argon shield, by 0.8g compound 5 and 0.124g2-(2-amino ethoxy) dissolve with ethanol in 6mL methylene dichloride, 45 DEG C of reactions 10 hours.Naturally cool to room temperature, add 0.09g sodium borohydride, stirring at normal temperature 1 hour.Wash reaction solution with water dichloromethane extraction, collect organic phase, anhydrous MgSO
4dry, filter, filtrate rotary evaporation also carries out column chromatography separation with methylene dichloride: methyl alcohol=10:1 as developping agent, obtains yellow-green colour solid.Wherein the mol ratio of compound 5,2-(2-amino ethoxy) ethanol, sodium borohydride and methylene dichloride is: 1:2:4:160;
9. synthetic compound 7
Under argon shield, 0.5g compound 6 and 0.33g compound b are dissolved in 3mL anhydrous methylene chloride, carefully add 0.014g trimethylsilyl trifluoromethanesulfonic acid fat, ice bath stirs 3 hours.Reaction finishes, and washes with 5% sodium bicarbonate aqueous solution, and dichloromethane extraction, collects organic phase, anhydrous MgSO
4dry, filter, by filtrate rotary evaporation, gained solid methylene dichloride: methyl alcohol=15:1 crosses post, obtains faint yellow solid.Wherein the mol ratio of compound 6, compound 2, trimethylsilyl trifluoromethanesulfonic acid fat and methylene dichloride is 1:2:0.2:140.
10. synthetic fluorescent chemicals
Under argon shield; 0.2g compound 7 is dissolved in the mixed solvent of 2mL methyl alcohol and 1mL tetrahydrofuran (THF); add sodium methylate 0.0093g; stirring at room temperature 5 hours; adding acidic cation-exchange resin to reaction solution is neutrality; being spin-dried for, is that developping agent is crossed post with methylene dichloride: methyl alcohol=4:1, obtains yellow-green colour solid.Wherein the mol ratio of compound 7, sodium methylate, methyl alcohol, tetrahydrofuran (THF) is 1:1.6:540:135.
2, prepare fluorescence sense film
Compound VI is dissolved in trichloromethane, is prepared into the storing solution of 0.18mg/mL.Get 30 μ L storing solutions and under the atmosphere of relative humidity 75%, be evenly coated in clean glass matrix surface, place and within 20 minutes, treat that its solvent evaporates is complete, sealing is preserved, and prepares fluorescence sense film.
Embodiment 3
1. synthetic iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(methoxyl group)-benzene
Under nitrogen protection atmosphere, in 140mL acetum, add respectively the aqueous sulfuric acid 15mL of 2.0g to anisole, 5g iodine, 0.61g Potassium Iodate and massfraction 10%.80 DEG C are stirred 10 hours, and by a large amount of solid suction filtrations that produce, vacuum-drying, obtains white solid.Be wherein 1:1:0.2:170:2 to the mol ratio of anisole, iodine, Potassium Iodate, acetic acid and the vitriol oil.
2. synthetic iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene
Under nitrogen protection, by 7.8g2, iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(methoxyl group)-benzene is dissolved in 50mL methylene dichloride, and under-78 DEG C of conditions, in solution, drips 7.44mL boron tribromide.After being added dropwise to complete, stirring at room temperature 12 hours, by a large amount of solid suction filtrations that produce, vacuum-drying, obtains white solid.Wherein, the mol ratio of iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(methoxyl group)-benzene, boron tribromide and methylene dichloride is 1:4:40;
3. synthetic compound 3
Under argon shield, by 6.0g cholesterol, 25.3g1,8 two bromooctanes and 4.4g potassium hydroxide are dissolved in 50mL anhydrous tetrahydro furan, react 16 hours at 80 DEG C.Rotary evaporation is except desolventizing, washing dichloromethane extraction, and rotary evaporation obtains yellow oil, and recrystallizing methanol is carried out column chromatography separation with methylene dichloride: sherwood oil=1:1, obtains white solid.Wherein the mol ratio of cholesterol, 1,8 two bromooctane, potassium hydroxide and tetrahydrofuran (THF) is 1:6:5:40;
4. synthetic compound 4
Under argon shield, by 5.4g compound 3,0.85g2, iodo-Isosorbide-5-Nitrae-bis-of 5-bis-(hydroxyl)-benzene, 8.0g salt of wormwood are dissolved in the anhydrous DMF of 30mL, react 16 hours at 160 DEG C.Reaction finishes, and solution is poured into water, and has a large amount of Precipitations, suction filtration, and vacuum-drying, carries out column chromatography separation with methylene dichloride: sherwood oil=3:2, obtains white solid.Wherein, the mol ratio of iodo-Isosorbide-5-Nitrae-bis-of 2,5-bis-(hydroxyl)-benzene, compound 3, salt of wormwood and DMF is 1:4:25:170;
5. synthetic compound 5
Under argon shield, 1.5g compound 4,0.58g are dissolved in the anhydrous Diisopropylamine of 7.8mL and 8.2mL dry toluene alkynyl phenyl aldehyde, 0.01g cuprous iodide, 0.064g tetraphenylphosphonium palladium.At 70 DEG C, react 12 hours.After reaction finishes, be cooled to room temperature, washing dichloromethane extraction, by organic phase rotary evaporation, recrystallizing methanol, gained yellow solid methylene dichloride: methyl alcohol=100:1 carries out column chromatography separation, obtains yellow-green colour solid.Wherein compound 4, be 1:4:0.05:0.05:50:70 to the mol ratio of acetylenylbenzene formaldehyde, cuprous iodide, tetraphenylphosphonium palladium, Diisopropylamine and toluene;
6. synthetic compound 1
Under nitrogen protection, 4g β-D alpha-glucose pentaacetate and 1.17g acetic acid hydrazine are dissolved in to 47mLN, in dinethylformamide, in 55 DEG C of reactions 3 hours.Reaction finishes, and the extraction of washing ethyl acetate, collects organic phase, and rotary evaporation obtains colorless oil.Wherein the mol ratio of β-D alpha-glucose pentaacetate, acetic acid hydrazine and DMF is 1:1.3:60;
7. synthetic compound 2
Under argon shield, 1.5g compound 1,2.46g Trichloroacetonitrile and 0.42g cesium carbonate are dissolved in 13.7mL anhydrous methylene chloride in 0 DEG C.Ice bath stirs 3 hours, by solid filtering, and filtrate rotary evaporation, gained oily matter ethyl acetate: sherwood oil=1:1 is that developping agent is crossed post, obtains faint yellow oily matter.Wherein the mol ratio of compound 1, Trichloroacetonitrile, cesium carbonate and methylene dichloride is 1:4:0.3:50;
8. synthetic compound 6
Under argon shield, by 0.8g compound 5 and 0.248g2-(2-amino ethoxy) dissolve with ethanol in 6mL methylene dichloride, 45 DEG C of reactions 10 hours.Naturally cool to room temperature, add 0.09g sodium borohydride, stirring at normal temperature 1 hour.Wash reaction solution with water dichloromethane extraction, collect organic phase, anhydrous MgSO
4dry, filter, filtrate rotary evaporation also carries out column chromatography separation with methylene dichloride: methyl alcohol=10:1 as developping agent, obtains yellow-green colour solid.Wherein the mol ratio of compound 5,2-(2-amino ethoxy) ethanol, sodium borohydride and methylene dichloride is 1:4:4:160;
9. synthetic compound 7
Under argon shield, 0.5g compound 6 and 0.66g compound 2 are dissolved in 3mL anhydrous methylene chloride, carefully add 0.014g trimethylsilyl trifluoromethanesulfonic acid fat, ice bath stirs 3 hours.Reaction finishes, and washes with 5% sodium bicarbonate aqueous solution, and dichloromethane extraction, collects organic phase, anhydrous MgSO
4dry, filter, by filtrate rotary evaporation, gained solid methylene dichloride: methyl alcohol=15:1 crosses post, obtains faint yellow solid.Wherein the mol ratio of compound 6, compound 2, trimethylsilyl trifluoromethanesulfonic acid fat and methylene dichloride is 1:4:0.2:140.
10. synthetic fluorescent chemicals
Under argon shield; 0.2g compound 7 is dissolved in the mixed solvent of 2mL methyl alcohol and 1mL tetrahydrofuran (THF); add sodium methylate 0.0039g; stirring at room temperature 5 hours; adding acidic cation-exchange resin to reaction solution is neutrality; being spin-dried for, is that developping agent is crossed post with methylene dichloride: methyl alcohol=4:1, obtains yellow-green colour solid.Wherein the mol ratio of compound 7, sodium methylate, methyl alcohol, tetrahydrofuran (THF) is 1:0.8:540:135.
2, prepare fluorescence sense film
Compound dissolution, in trichloromethane, is prepared into the storing solution of 1.8mg/mL.Get 50 μ L storing solutions and under the atmosphere of relative humidity 75%, be evenly coated in clean glass matrix surface, place and within 60 minutes, treat that its solvent evaporates is complete, sealing is preserved, and prepares fluorescence sense film.
Embodiment 4
In embodiment 1～3 preparation containing cholesterol, sugared structure fluorescent chemicals synthetic compound 3 steps 3. in, dibromo substituted straight chain alkane used is replaced with equimolar pentamethylene bromide, and other steps of this step are identical with corresponding embodiment, prepare compound 3, in formula, the value of n is 5.Synthetic compound 7 steps 8. in, 2-(2-amino ethoxy) equimolar 2-[2-for ethanol (2-amino ethoxy) used] replace, in formula, the value of m is 2, and other steps of this step are identical with corresponding embodiment, prepare compound 7.Synthetic compound 1 step 6. in, β-D alpha-glucose pentaacetate used is replaced with equimolar α-D alpha-glucose pentaacetate, prepares compound 1.
Other steps are identical with embodiment 1～3.
Embodiment 5
In embodiment 1～3 preparation containing cholesterol, sugared structure fluorescent chemicals synthetic compound 3 steps 3. in, used 1,8-bis-bromooctanes are with equimolar 1,10-dibromo-decane is replaced, other steps of this step are identical with corresponding embodiment, prepare compound 3, and in formula, the value of n is 10.Synthetic compound 7 steps 8. in, 2-(2-amino ethoxy) ethanol used is replaced with equimolar 2-monoethanolamine, in formula, the value of m is 0.Other steps of this step are identical with corresponding embodiment, prepare compound 7.Synthetic compound 1 step 6. in, β-D alpha-glucose pentaacetate used is replaced with equimolar β-D semi-lactosi pentaacetate, prepares compound 1.
Other steps are identical with embodiment 1～3.
Embodiment 6
In embodiment 1～3 preparation containing cholesterol, sugared structure fluorescent chemicals synthetic compound 3 steps 3. in, used 1,8-bis-bromooctanes are with equimolar 1,12-dibromo-dodecane is replaced, other steps of this step are identical with corresponding embodiment, prepare compound 3, and in formula, the value of n is 12.Synthetic compound 1 step 6. in, β-D alpha-glucose pentaacetate used is replaced with equimolar β-L semi-lactosi pentaacetate, prepares compound 1.Other steps are identical with embodiment 1～3.
Embodiment 7
In embodiment 1～3 preparation containing cholesterol, sugared structure fluorescent chemicals synthetic compound 1 step 6. in, β-D alpha-glucose pentaacetate used is replaced with equimolar α-D seminose pentaacetate, prepares compound 1.Other steps are identical with embodiment 1～3.
Embodiment 8
Prepare in fluorescence sense film step 2 at embodiment 1～3, storing solution solvent for use trichloromethane is replaced with tetrahydrofuran (THF).Other steps are identical with embodiment 1～3.
Embodiment 9
Prepare in fluorescence sense film step 2 at embodiment 1～3, by clean glass matrix used at 98%H
2sO
4(21mL) and 30%H
2o
2(9mL) in mixing solutions, heat 1 hour under slight boiling condition, a large amount of intermediate waters of cooling rear use rinse, and dry up stand-by.Other steps are identical with embodiment 1～3.
Claims (10)
1. a fluorescent chemicals, is characterized in that, the structural formula of this fluorescent chemicals is as follows:
Wherein, m=0,1 or 2, n=5,8,10 or 12.
2. a preparation method for fluorescent chemicals, is characterized in that, comprises the following steps:
1), under nitrogen protection, sugared pentaacetate and acetic acid hydrazine are dissolved in DMF, at 50～60 DEG C, stir 2～4 hours, in the reaction solution obtaining, add ethyl acetate after washing, collect organic phase, except desolventizing obtains colorless oil, i.e. compound 1;
2), under argon shield, compound 1, Trichloroacetonitrile and cesium carbonate are dissolved in anhydrous methylene chloride in 0 DEG C, 0 DEG C of insulation reaction 1～3 hour, the solid filtering that reaction is produced, filtrate is condensed into oily matter, and oily matter is carried out to column chromatography separation, obtains compound 2;
3) under argon shield, compound 5 and amino ethoxy ethanol substituent are dissolved in methylene dichloride, stir 16～20 hours at 40～50 DEG C; naturally cool to room temperature, add sodium borohydride, stirring at normal temperature reaction 1～2 hour; reaction finishes after washing; use again dichloromethane extraction, collect organic phase, then organic phase is dried and is filtered; filtrate is except desolventizing and carry out column chromatography separation; obtain yellow-green colour solid 6, wherein, the structural formula of described compound 5 is:
The structural formula of described amino ethoxy ethanol substituent is:
4) under argon shield, yellow-green colour solid 6 and compound 2 are dissolved in anhydrous methylene chloride, add trimethylsilyl trifluoromethanesulfonic acid fat, ice bath stirred after 2～4 hours, washed with the sodium bicarbonate aqueous solution that mass concentration is 5%, used dichloromethane extraction, collect organic phase, then organic phase is dried and is filtered, filtrate, except the laggard row column chromatography of desolventizing separates, obtains flaxen compound 7;
5) under argon shield; compound 7 is dissolved in the mixed solvent of methyl alcohol and tetrahydrofuran (THF); drip sodium methoxide solution; under room temperature, stir 4～6 hours; it is neutral adding acidic cation-exchange resin to reaction solution, obtains mixed solution, this mixed solution is removed to the laggard row column chromatography of desolventizing and separate; obtain yellow-green colour solid, i.e. fluorescent chemicals.
3. the preparation method of a kind of fluorescent chemicals according to claim 2, is characterized in that step 1) in, the mol ratio of sugared pentaacetate, acetic acid hydrazine and DMF is 1:(1～1.3).
4. according to the preparation method of a kind of fluorescent chemicals described in claim 2 or 3, it is characterized in that, described sugared pentaacetate is β-D alpha-glucose pentaacetate, α-D alpha-glucose pentaacetate, β-D semi-lactosi pentaacetate, β-L semi-lactosi pentaacetate or α-D seminose pentaacetate.
5. the preparation method of a kind of fluorescent chemicals according to claim 2, is characterized in that step 2) in, the mol ratio of compound 1, Trichloroacetonitrile and cesium carbonate is 1:(2～4): (0.2～0.4); Step 2) described column chromatography separates and adopts the volume ratio of ethyl acetate: sherwood oil=1:1 to mix the eluent making to separate.
6. the preparation method of a kind of fluorescent chemicals according to claim 2, is characterized in that step 3) in, the mol ratio of compound 5, amino ethoxy ethanol substituent and sodium borohydride is 1:(2.5～4): (3～5); Step 3) described column chromatography separates and adopts the volume ratio of methylene dichloride: methyl alcohol=10:1 to mix the eluent making to separate.
7. the preparation method of a kind of fluorescent chemicals according to claim 2, is characterized in that step 4) in, the mol ratio of compound 6, compound 2 and trimethylsilyl trifluoromethanesulfonic acid fat is 1:(2～4): (0.1～0.3); Step 4) described column chromatography separates and adopts the volume ratio of methylene dichloride: methyl alcohol=15:1 to mix the eluent making to separate.
8. the preparation method of a kind of fluorescent chemicals according to claim 2, it is characterized in that, step 5) in, in compound 7, sodium methoxide solution, the mol ratio of sodium methylate, methyl alcohol and tetrahydrofuran (THF) is 1:(0.8～1.6): (500～600): (100～150); Chromatographic column separation adopts the volume ratio of methylene dichloride: methyl alcohol=4:1 to mix the eluent making and separates.
9. adopt fluorescent chemicals described in right 1 to prepare a method for fluorescence sense film, it is characterized in that, comprise the following steps:
1) fluorescent chemicals is dissolved in trichloromethane, makes the storing solution that concentration is 0.18mg/mL～1.80mg/mL;
2) under the atmosphere that is 60%～75% in relative humidity, the storing solution that is 0.18mg/mL～1.80mg/mL by concentration is coated in clean glass matrix surface uniformly, leaves standstill 20～60min, makes fluorescence sense film.
10. a fluorescence sense film claimed in claim 9 is in the application of preparing in fluorescence sense device.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109715066A (en) * | 2016-07-20 | 2019-05-03 | 巴尔的摩马里兰大学 | Fluoremetry and haptic lens based on siloxanes aquogel |
| CN110204733A (en) * | 2019-05-28 | 2019-09-06 | 长安大学 | A kind of α-mannose-modified to-receptor type bioabsorbable polymer material and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102539399A (en) * | 2011-12-16 | 2012-07-04 | 陕西师范大学 | Preparation method and application of cholesterol-containing conjugated oligomer monomolecular layer fluorescence sensing thin film |
| CN102604140A (en) * | 2012-03-21 | 2012-07-25 | 陕西师范大学 | Preparation method of polymer fluorescence sensing film containing cholesterol |
| CN102753562A (en) * | 2009-12-14 | 2012-10-24 | 巴塞尔大学 | Mannose derivatives as antagonists of bacterial adhesion |
-
2014
- 2014-06-04 CN CN201410245243.1A patent/CN104031108B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102753562A (en) * | 2009-12-14 | 2012-10-24 | 巴塞尔大学 | Mannose derivatives as antagonists of bacterial adhesion |
| CN102539399A (en) * | 2011-12-16 | 2012-07-04 | 陕西师范大学 | Preparation method and application of cholesterol-containing conjugated oligomer monomolecular layer fluorescence sensing thin film |
| CN102604140A (en) * | 2012-03-21 | 2012-07-25 | 陕西师范大学 | Preparation method of polymer fluorescence sensing film containing cholesterol |
Non-Patent Citations (1)
| Title |
|---|
| 晏妮: "含糖荧光活性小分子胶凝剂的自组装行为及其结构依赖性", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109715066A (en) * | 2016-07-20 | 2019-05-03 | 巴尔的摩马里兰大学 | Fluoremetry and haptic lens based on siloxanes aquogel |
| CN109715066B (en) * | 2016-07-20 | 2022-04-05 | 巴尔的摩马里兰大学 | Silicone hydrogel based fluorescence assays and contact lenses |
| CN110204733A (en) * | 2019-05-28 | 2019-09-06 | 长安大学 | A kind of α-mannose-modified to-receptor type bioabsorbable polymer material and its preparation method and application |
| CN110204733B (en) * | 2019-05-28 | 2021-07-02 | 长安大学 | Alpha-mannose modified donor-receptor type biopolymer material and preparation method and application thereof |
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