CN105820183A - Boron dipyrromethene compound containing alpha,beta-unsaturated ketone, and application of same in detection of sulfite - Google Patents
Boron dipyrromethene compound containing alpha,beta-unsaturated ketone, and application of same in detection of sulfite Download PDFInfo
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Abstract
The invention relates to a boron dipyrromethene compound containing alpha,beta-unsaturated ketone, and application of same in detection of sulfite. A novel fluorescent probe utilizes the characteristic that C-C double bonds on the alpha,beta-unsaturated ketone and sulfite undergo nucleophilic addition; after reaction with sulfite, the absorption and emission spectra of the compound both show substantial blue shift; and the probe has high detection sensitivity and selectivity to sulfite, has emission wavelength of 620 nm, is located in a red light zone and is applicable to detection of sulfite in a practical sample.
Description
Technical field
The present invention relates to sulphite detection technique field, specifically, be a kind of containing α, alpha, beta-unsaturated ketone fluorine boron pyroles and the application in sulphite detects thereof.
Background technology
Various forms of sulphite (sulfur dioxide, sulfurous acid, sulphite etc.) be the most widely used food of class, beverage preservative with protection food not oxidized; also contribute to prevent the microorganism continued growth of food simultaneously; extend the holding time of food; additionally; sulphite in daily life can be as bleach, preservative and antioxidant, at aspects such as dyestuff, papermaking, process hides and organic synthesiss as reducing agent etc..But, sulfite ion is irritant to skin, eye, respiratory tract.Research finds, certain density sulphite may cause asthma or the anaphylaxis of some crowds.Meanwhile, the sulphite that commercial production discharge a large amount of exist with sulfur dioxide form are the main pollutions of environment, are also the main causes of global warming.In view of the toxicity of sulphite, various countries launch respectively various statutory standard to limit the use of sulphite.
Fluorescent probe analytical technology has highly sensitive, the feature of good operability, and fluorescent spectrometry has a wide range of applications in a lot of fields because of advantages such as it are convenient, lossless, real-time, quick, sensitive.The sulphite colorimetric design, synthesized or fluorescent probe are based primarily upon the chelation of sulphite and metal ion and amine forms complex or the selectivity addition utilizing sulphite and aldehyde and to mechanism such as the selectivity deprotections of levulinate.But simply there is color or the change of fluorescence intensity in above-mentioned big multiprobe, its detection sensitivity is relatively low when responding sulphite, thereby increases and it is possible to because sample environment or concentration and probe concentration change cause the fluctuation of measurement signal, thus cause the reduction of measurement accuracy.
On the contrary, scale fluorescence probe is provided that the change of stable self-correcting signal, environment or sample concentration is less on the impact of testing result, and its detection sensitivity is also high than pure Strength Changes probe, has higher application prospect.
Therefore, the analysis method developing selective enumeration method food highly sensitive, high or environment sulfite salt content has very important significance.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of long transmitted wave length, Ratio-type contain α, alpha, beta-unsaturated ketone fluorine boron azole compounds and the application in sulphite detects thereof.
A first aspect of the present invention, it is provided that a kind of fluorine boron azoles, it is characterised in that its general structure:
In formula: R1、R2Shown in formula structured as described above；R3For alkyl, hydroxyl, amino or halogen.
A second aspect of the present invention, it is provided that described in a kind of first aspect present invention containing α, the synthetic method of alpha, beta-unsaturated ketone fluorine boron azoles, it is characterised in that it concretely comprises the following steps:
(1) by solvent, benzaldehyde, pyrroles joins in reactor, then drips several hydrochloric acid, and wherein the mol ratio of benzaldehyde and pyrroles is 1:1～1:6, preferably 1:3；Benzaldehyde is 7～9:100～150 with the mol ratio of solvent, preferably 7:110；After mixture ice bath is reacted 2～8 hours, filter, by ultra-pure water and petroleum ether, obtain celadon solid, be dried；Crude on silica gel post separates, and rotation boils off solvent, obtains faint yellow solid 1；
Described solvent is water, methanol, ethanol, acetonitrile, dimethylformamide or their mixed solvent；
(2) in nitrogen protection, dropwise dripping phosphorus oxychloride under ice bath in organic solvent, wherein, the volume ratio of phosphorus oxychloride and solvent is 1:1～1:30, preferably 1:7；Reacting 30min at-25～25 DEG C, then rapidly join in above-mentioned solution by the dichloromethane solution dissolved with the faint yellow solid 1 obtained by step (1), wherein, the molal volume of faint yellow solid 1 and dichloromethane ratio is for 1:3～1:30, preferably 1:8；Then being poured into by reactant liquor in the dichloromethane of two volumes, regulate pH to about 9 by NaOH solution, organic facies saturated aqueous common salt extracts 3 times, then uses anhydrous Na2SO4It is dried；Vacuum rotary steam removes CH2Cl2, it was spin-dried for silicagel column, obtained pale pink solid 2；
Described solvent is ethanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, and/or oxolane；
(3) the pale pink solid 2 that step (2) obtains is added to organic solvent, add 2 under ice bath, 3-bis-chloro-5,6-dicyano benzoquinone (DDQ), wherein, the mol ratio of pale pink solid 2 and DDQ is 1:0.5～1:3, preferably 1:1.2；The molal volume of pale pink solid 2 and solvent is than for 1:10～1:50, preferably 1:30；After reaction 20min, question response liquid warms naturally to room temperature；Being sequentially added into triethylamine and boron trifluoride diethyl etherate to above-mentioned system, wherein, the volume ratio of triethylamine and boron trifluoride diethyl etherate is 1:0.5～1:3, preferably 1:1；Continuing stirring 15min, extract described solution with the dichloromethane of above-mentioned solution twice equivalent, organic facies is dried after washing by saturated aqueous common salt organic facies, was spin-dried for silicagel column, and obtained red solid 3.
Described solvent is ethanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, oxolane, and/or dichloromethane；
(4) red solid 3 that step (3) obtains is dissolved in mixed solvent, in above-mentioned solution, 4-acetylpyridine and pyrrolidine is added under room temperature, wherein, the molal volume of red solid 3 and mixed solvent is than for 1:100～1:300, preferably 1:150；The mol ratio of red solid 3 and 4-acetylpyridine is 1:1～1:5, preferably 1:1.8；Red solid 3 and pyrrole press against the molal volume of alkane than for 1:0.5～1:5, preferably 1:1.5；Room temperature reaction 1～10 days, be spin-dried for reactant liquor.Cross silicagel column, obtain red brown solid 4；
Described mixed solvent is the mixed solution of ethanol or methanol and dichloromethane, and its volume ratio is 1:1～1:5；
(5) being dissolved in solvent by the red brown solid 4 that step (4) obtains, under nitrogen protection, room temperature gradually drips iodomethane in mixed liquor, and wherein, the molal volume of red brown solid 4 and solvent is than for 1:20～1:300, preferably 1:100；The mol ratio of red brown solid 4 and iodomethane is 1:1～1:30, preferably 1:10；The reaction of above-mentioned solution at room temperature lucifuge is disappeared to raw material, is spin-dried for reactant liquor.Cross silicagel column, obtain violet solid and be target product；
Described solvent is ethanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, oxolane, dichloromethane.
In another preference, described benzaldehyde and the mol ratio of pyrroles are 1:3.
In another preference, in described step (1), described solvent is water, methanol, ethanol, acetonitrile, dimethylformamide or their mixed solvent.
In another preference, in step (4), the mol ratio of described red solid 3 and 4-acetylpyridine is 1:1.8.
A third aspect of the present invention, it is provided that a kind of containing α, the application in sulphite detects of the alpha, beta-unsaturated ketone fluorine boron pyroles, it concretely comprises the following steps:
(1) preparation is containing α, DMF or the DMSO solution of alpha, beta-unsaturated ketone fluorine boron azoles, for storing solution 1；
(2) sulphite (SO is prepared3 2-) and phosphate buffer solution (pH7.4,20mM) respectively storing solution 2 and the storing solution 3 of CTAB；
(3) accurately pipetting in the volumetric flask of 33.3 μ L storing solution 1 to 10mL, 20mM phosphate buffer solution or storing solution 3 with pH7.4 are diluted to scale, add 166.7 μ L storing solutions 2 in above-mentioned solution so that SO3 2-Ultimate density be 500 μMs, test solution, in the ultraviolet of different time and fluorescence spectrum, is sulphite to containing α, the time titration curve of alpha, beta-unsaturated ketone fluorine boron azoles.
(4) accurately pipette in the volumetric flask of 33.3 μ L storing solution 1 to 10mL, be diluted to scale with the phosphate buffer solution (PH7.4) of 20mM or storing solution 3, then drip storing solution 2 in above-mentioned solution so that SO3 2-Ultimate density be 1～500 μM, test solution is at variable concentrations SO3 2-In the presence of ultraviolet and fluorescence spectrum, be sulphite to α, the concentration titrations curve of alpha, beta-unsaturated ketone fluorine boron azoles.
(5) accurately pipette in the volumetric flask of 33.3 μ L storing solution 1 to 10mL, 0.5g white sugar or 100 μ L white wines is added to volumetric flask, phosphate buffer solution (PH7.4) or storing solution 3 with 20mM are diluted to scale, it is separately added into 0 again, 16.7 μ L and the storing solution 2 of 33.3 μ L, measure ultraviolet and the fluorescence spectrum of each test solution.By acquired results and the standard curve control obtained by step (4), try to achieve white sugar and the content of white wine sulfite salt.
In should be understood that within the scope of the present invention, can be combined with each other between above-mentioned each technical characteristic and each technical characteristic specifically described in below (eg embodiment) of the present invention, thus constitute new or preferred technical scheme.As space is limited, the most tired at this state.
Accompanying drawing explanation
Fig. 1 is the molecular structural formula of BSP1 and BSP2.
Fig. 2 is the synthetic route of compound BSP1 and BSP2
Fig. 3 is variable concentrations SO3 2-Impact on probe BSP1 absorption spectrum (a) He emission spectrum (b)；CTAB-phosphate buffer solution (PH7.4,20mM), [BSP1]=10uM, [CTAB]=1mM, fluorescence exciting wavelength is 512nm.
Fig. 4 is fluorescence ratio (I554/I618) with the change curve of sulfite concentration；CTAB-phosphate buffer solution (PH7.4,20mM), [BSP1]=10uM, [CTAB]=1mM, fluorescence exciting wavelength is 512nm.
Fig. 5 is control compound structure chart.
Table 1 white sugar and the content of wine sulfite salt
Detailed description of the invention
Fluorine boron pyrrole is pressed against class fluorescent probe and is had highly sensitive, specific recognition, absorb and launch the advantages such as wavelength length, chromophore conventional when being fluorescent probe molecule design.By by α, alpha, beta-unsaturated ketone conjugation is connected to fluorine boron pyrrole and presses against the conjugated system that can extend compound on molecule so that absorption maximum and transmitting red shift of wavelength.When, after probe molecule with sulphite generation nucleophilic addition, conjugated system shortens, cause the absorption of compound and launch the notable blue shift of wavelength, thus realizing the detection to sulphite.
Compared with prior art, the positive effect of the present invention is:
Novel fluorescent probe molecule has longer transmitting wavelength and is positioned near infrared region, is conducive to eliminating the interference of background, and is the fluorescent probe of Ratio-type, has more preferable selectivity and higher susceptiveness.Aqueous surfactant solution system is used to replace organic solvent to decrease the pollution of test process team environment.Under physiological ph conditions (pH=7.4), such probe has the highest spectral response to sulphite, to the micromolecular compound such as hydrogen sulfide, mercaptan and other aniones of other sulfur-bearings substantially without response.
Presented below a kind of containing alpha, beta-unsaturated ketone fluorine boron azoles and sulphite detect in application detailed description of the invention:
Embodiment 1:
1. the synthesis of compound BSP1 and BSP2:
(1) synthesis of compound 1: weigh 1.0g benzaldehyde (9.43mmol) and 1.9g pyrroles (28.29mmol) in the single port flask of 250mL, add the ultra-pure water of 150mL, lower 7～8 hydrochloric acid of dropping of stirring, solution quickly becomes milky, and above-mentioned reactant liquor stirs in ice bath 4h, TLC follows the tracks of reaction and disappears to raw material, solution there is a large amount of solid separate out, filter, with ultra-pure water and petroleum ether solid, obtain celadon solid, product anhydrous Na2SO4It is dried；Crude on silica gel post separates (petroleum ether: dichloromethane=1:1), and rotation boils off solvent, obtains 1.79g faint yellow solid.1HNMR(400MHz,CDCl3) δ (ppm): 9.51 (s, 2H), 8.93～8.80 (m, 6H), 8.28 (s, 2H), 7.75 (d, J=2.69Hz, 2H), 7.51 (s, 2H).
(2) synthesis of compound 2:
3.7mLDMF, N is added in 100mL there-necked flask20.5mLPOCl is drawn with needle tubing under protection3It is slowly added dropwise to above-mentioned flask, at-25～25 DEG C, reacts 30min, then will be dissolved with the CH of the 36mL of 2g (4.51mmol) phenyl dipyrrylmethanes (compound 1)2Cl2Solution needle tubing is quickly added in above-mentioned flask.Solution colour is become bronzing from colourless, continues reaction 3h at 0 DEG C, and some plate (petroleum ether: ethyl acetate=50:35) disappears to raw material point, and reactant liquor is poured into the CH of 65mL2Cl2In, regulating PH to about 9 by NaOH solution, retain organic facies, the saturated aqueous common salt of organic facies 100mL extracts 3 times, then uses anhydrous Na2SO4It is dried；Vacuum rotary steam removes CH2Cl2, cross silicagel column (petroleum ether: ethyl acetate=50:10), obtain light powder solid 400mg.1HNMR(400MHz,CDCl3) δ (ppm): 9.32 (s, 1H), 7.34～7.17 (m, 5H), 6.90 (s, 1H), 6.72 (s, 1H), 6.16 (s, 1H), 6.10 (s, 1H), 5.97 (s, 1H), 5.52 (s, 1H).
(3) synthesis of compound 3:
The compound 2 weighing 400mg (1.6mmol) joins the CH equipped with 50mL2Cl2Round-bottomed flask in, 400mg2 is added in ice bath downhill reaction liquid, 3-bis-chloro-5,6-dicyano benzoquinone (DDQ, 1.76mmol), in flask, the triethylamine of 1.6mL and the boron trifluoride diethyl etherate of 1.6mL is added again after reaction 20min, 15min is stirred at room temperature, and some plate (petroleum ether: ethyl acetate=50:35), after raw material point disappears, reactant liquor saturated aqueous common salt is extracted 3 times, then uses anhydrous Na2SO4It is dried；Vacuum rotary steam removes CH2Cl2, cross silicagel column (petroleum ether: CH2Cl2=1:1), obtain the solid of redness.1HNMR(400MHz,CDCl3) δ (ppm): 10.37 (s, 1H), 8.21 (s, 1H), 7.62～7.55 (m, 5H), 7.13 (d, J=4.57,1H), 7.08 (d, J=4.34,1H), 6.84 (d, J=4.35,1H), 6.72 (d, J=4.67,1H)；MS measured value m/z:319.1 (M+Na)+, value of calculation C16H11BF2N2O(M+Na)+:319.09.
(4) synthesis of BSP1:
Weighing the compound 3 of 100mg (0.34mmol), the 4-acetylpyridine of 73.64g (0.61mmol) is dissolved in the solvent (EtOH:CH equipped with 60mL2Cl2=1:2) single port flask in, lower addition 7～8 droplet pyrrolidines are stirred at room temperature, react 1～10 day, put plate (CH2Cl2: MeOH=50:1) to the disappearance of raw material point.Rotary evaporation removes solvent, crosses silicagel column, obtains the red brown solid of 60mg.1HNMR(400MHz,CDCl3) δ (ppm): 9.64 (d, J=5.85,2H), 9.17 (d, J=15.65,1H), 8.62 (d, J=5.99,2H), 8.32～8.26 (m, 6H), 8.15 (s, 1H), 7.82 (d, J=4.07,1H), 7.75 (d, J=5.19,1H), 7.20 (d, J=4.04,1H), 7.15 (d, J=5.19,1H)；13CNMR(400MHz,DMSO-d6) δ (ppm): 188.9,161.8,151.7,145.3,139.2,138.0,137.2,137.1,136.1,13 5.1,131.4,130.1,129.6,126.9,122.5,120.7,119.2,118.1,117. 9.
(5) synthesis of probe BSP2:
The BSP1 weighing 100mg (0.25mmol) is dissolved in the acetonitrile of 25mL, under nitrogen protection, adds the iodomethane of excess, and under room temperature, lucifuge is reacted 5～20 days, puts plate (CH2Cl2: MeOH=50:1) to the disappearance of raw material point.Rotary evaporation removes solvent, crosses silicagel column, obtains the violet solid of 50mg.1HNMR(CD3OD, 400MHz) δ (ppm): 9.07 (d, J=6.59,2H), 8.56 (d, J=6.67,2H), 8.45 (d, J=15.15,1H), 7.60～7.45 (m, 7H), 7.28 (d, J=4.12,1H), 6.98 (d, J=5.33,1H), 6.69 (d, J=5.35,1H), 6.31 (d, J=4.09,1H), 4.47 (s, 7H)；13CNMR(400MHz,CD3OD)δ(ppm):184.8,182.0,152.3,147.1,140.1,138.9,135.8,135.0,130.8,130.3,129.4,128.8,127.9,126.9,126.3,125.5,119.5,118.2,117.8,116.3.
Embodiment 2
Buffer solution-CTAB system of determination sulphite:
Accurately weigh a certain amount of compound BSP1 and be dissolved in 10mLN, dinethylformamide prepares the storing solution cryopreservation of 30mM；Accurately weigh a certain amount of SO3 2-It is dissolved in 10mL phosphate buffer solution (PBS, 20mM, pH=7.4), prepares the sulphite storing solution of 30mM；The CTAB accurately weighing certain mass is dissolved in 10mL buffer solution, prepares the CTAB-PBS stock solution of 1mM.Accurately pipette the storing solution of 33.3 μ L compound BSP1 in 10mL volumetric flask, be diluted to scale with CTAB-PBS storing solution, obtain the buffer solution of 10 μMs of BSP1.In above-mentioned solution, add the sulphite storing solution of 167 μ L, measure probe solution fluorescence and ultraviolet spectra under different time, process through data and can obtain probe BSP1 at CTAB buffer solution system curve time response to sulphite.The sulphite storing solution of different volumes (1～500 μM) is dripped in probe-CTAB phosphate buffer solution, measure variable concentrations sulphite to probe solution fluorescence and the impact of ultraviolet spectra, process through data and can obtain probe BSP1 at the buffer solution system concentration-response curve to sulphite.
Sulphite in buffer solution-CTAB system of determination white sugar or white wine
Accurately pipette in the volumetric flask of 33.3 μ L storing solution 1 to 10mL, it is added thereto to 0.5g white sugar or 100 μ L white wines again, phosphate buffer solution (PH7.4) or storing solution 3 with 20mM are diluted to scale, it is separately added into 0,16.7 μ L and the storing solution 2 of 33.3 μ L, measure ultraviolet and the fluorescence spectrum of each test solution.The sulfite content in white sugar or white wine and after mark-on is tried to achieve by above-mentioned concentration-response curve.
Table 1 white sugar and the mensuration of white wine sulfite salt content
Reference examples 1
At present the sulphite fluorescent probe of document report is primarily present following 2 deficiencies: 1) detect in the presence of the organic solvent of higher proportion, probe1 as shown in Figure 5, at DMSO: the solvent of water=1:1 realizes the detection (X.Gu to sulphite, C.Liu, Y.-C.Zhu .Y.-Z.Zhu, J.Agric.FoodChem.2011,59,11,935 11939)；2) launch wavelength shorter, such as coumarin kind compound probe2, in the solvent of DMSO:PBS=3:7 with the transmitted wave of sulphite product a length of 477nm (Z.Liu, S.Guo, J.Piao, X.Zhou, X.Wu, RSCAdv., 2014,4,54,554 54557).The present embodiment replaces organic solvent to reduce the pollution to environment with aqueous surfactant solution for detection system, transmitting wavelength before and after additionally probe reacts with sulphite is the longest (respectively 618nm and 554nm), and the detection of actual sample and Biosample sulfite salt is being had potential application.
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be regarded as in protection scope of the present invention.
Claims (6)
1. a fluorine boron azoles, it is characterised in that its general structure:
In formula: R1、R2Shown in formula structured as described above；R3For alkyl, hydroxyl, amino or halogen.
2. contain a α as claimed in claim 1, the synthetic method of alpha, beta-unsaturated ketone fluorine boron azoles, it is characterised in that it concretely comprises the following steps:
(1) by solvent, benzaldehyde, pyrroles joins in reactor, then drips several hydrochloric acid, and wherein the mol ratio of benzaldehyde and pyrroles is 1:1～1:6, preferably 1:3；Benzaldehyde is 7～9:100～150 with the mol ratio of solvent, preferably 7:110；After mixture ice bath is reacted 2～8 hours, filter, by ultra-pure water and petroleum ether, obtain celadon solid, be dried；Crude on silica gel post separates, and rotation boils off solvent, obtains faint yellow solid 1；
Described solvent is water, methanol, ethanol, acetonitrile, dimethylformamide or their mixed solvent；
(2) in nitrogen protection, dropwise dripping phosphorus oxychloride under ice bath in organic solvent, wherein, the volume ratio of phosphorus oxychloride and solvent is 1:1～1:30, preferably 1:7；Reacting 30min at-25～25 DEG C, then rapidly join in above-mentioned solution by the dichloromethane solution dissolved with the faint yellow solid 1 obtained by step (1), wherein, the molal volume of faint yellow solid 1 and dichloromethane ratio is for 1:3～1:30, preferably 1:8；Then being poured into by reactant liquor in the dichloromethane of two volumes, regulate pH to about 9 by NaOH solution, organic facies saturated aqueous common salt extracts 3 times, then uses anhydrous Na2SO4It is dried；Vacuum rotary steam removes CH2Cl2, it was spin-dried for silicagel column, obtained pale pink solid 2；
Described solvent is ethanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, and/or oxolane；
(3) the pale pink solid 2 that step (2) obtains is added to organic solvent, add 2 under ice bath, 3-bis-chloro-5,6-dicyano benzoquinone (DDQ), wherein, the mol ratio of pale pink solid 2 and DDQ is 1:0.5～1:3, preferably 1:1.2；The molal volume of pale pink solid 2 and solvent is than for 1:10～1:50, preferably 1:30；After reaction 20min, question response liquid warms naturally to room temperature；Being sequentially added into triethylamine and boron trifluoride diethyl etherate to above-mentioned system, wherein, the volume ratio of triethylamine and boron trifluoride diethyl etherate is 1:0.5～1:3, preferably 1:1；Continuing stirring 15min, extract described solution with the dichloromethane of above-mentioned solution twice equivalent, organic facies is dried after washing by saturated aqueous common salt organic facies, was spin-dried for silicagel column, and obtained red solid 3.
Described solvent is ethanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, oxolane, and/or dichloromethane；
(4) red solid 3 that step (3) obtains is dissolved in mixed solvent, in above-mentioned solution, 4-acetylpyridine and pyrrolidine is added under room temperature, wherein, the molal volume of red solid 3 and mixed solvent is than for 1:100～1:300, preferably 1:150；The mol ratio of red solid 3 and 4-acetylpyridine is 1:1～1:5, preferably 1:1.8；Red solid 3 and pyrrole press against the molal volume of alkane than for 1:0.5～1:5, preferably 1:1.5；Room temperature reaction 1～10 days, be spin-dried for reactant liquor.Cross silicagel column, obtain red brown solid 4；
Described mixed solvent is the mixed solution of ethanol or methanol and dichloromethane, and its volume ratio is 1:1～1:5；
(5) being dissolved in solvent by the red brown solid 4 that step (4) obtains, under nitrogen protection, room temperature gradually drips iodomethane in mixed liquor, and wherein, the molal volume of red brown solid 4 and solvent is than for 1:20～1:300, preferably 1:100；The mol ratio of red brown solid 4 and iodomethane is 1:1～1:30, preferably 1:10；The reaction of above-mentioned solution at room temperature lucifuge is disappeared to raw material, is spin-dried for reactant liquor.Cross silicagel column, obtain violet solid and be target product；
Described solvent is ethanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, oxolane, dichloromethane.
3. synthetic method as claimed in claim 2, it is characterised in that in step (1), described benzaldehyde and the mol ratio of pyrroles are 1:3.
4. as claimed in claim 2 containing α, the synthetic method of alpha, beta-unsaturated ketone fluorine boron azoles, it is characterized in that, in described step (1), described solvent is water, methanol, ethanol, acetonitrile, dimethylformamide or their mixed solvent.
5. as claimed in claim 2 containing α, the synthetic method of alpha, beta-unsaturated ketone fluorine boron azoles, it is characterised in that in step (4), the mol ratio of described red solid 3 and 4-acetylpyridine is 1:1.8.
6. containing a α, the application in sulphite detects of the alpha, beta-unsaturated ketone fluorine boron pyroles, it concretely comprises the following steps:
(1) preparation is containing α, DMF or the DMSO solution of alpha, beta-unsaturated ketone fluorine boron azoles, for storing solution 1；
(2) sulphite (SO is prepared3 2-) and phosphate buffer solution (pH7.4,20mM) respectively storing solution 2 and the storing solution 3 of CTAB；
(3) accurately pipetting in the volumetric flask of 33.3 μ L storing solution 1 to 10mL, 20mM phosphate buffer solution or storing solution 3 with pH7.4 are diluted to scale, add 166.7 μ L storing solutions 2 in above-mentioned solution so that SO3 2-Ultimate density be 500 μMs, test solution, in the ultraviolet of different time and fluorescence spectrum, is sulphite to containing α, the time titration curve of alpha, beta-unsaturated ketone fluorine boron azoles.
(4) accurately pipette in the volumetric flask of 33.3 μ L storing solution 1 to 10mL, be diluted to scale with the phosphate buffer solution (PH7.4) of 20mM or storing solution 3, then drip storing solution 2 in above-mentioned solution so that SO3 2-Ultimate density be 1～500 μM, test solution is at variable concentrations SO3 2-In the presence of ultraviolet and fluorescence spectrum, be sulphite to α, the concentration titrations curve of alpha, beta-unsaturated ketone fluorine boron azoles.
(5) accurately pipette in the volumetric flask of 33.3 μ L storing solution 1 to 10mL, it is added thereto to 0.5g white sugar or 100 μ L white wines again, phosphate buffer solution (PH7.4) or storing solution 3 with 20mM are diluted to scale, it is separately added into 0,16.7 μ L and the storing solution 2 of 33.3 μ L, measure ultraviolet and the fluorescence spectrum of each test solution.By acquired results and the standard curve control obtained by step (4), try to achieve white sugar and the content of white wine sulfite salt.
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| CN106674183A (en) * | 2016-12-29 | 2017-05-17 | 济南大学 | Novel ratio type sulfite fluorescent probe as well as preparation method and biological application thereof |
| CN109053778A (en) * | 2018-06-14 | 2018-12-21 | 忻州师范学院 | The reagent and its synthetic method of specific detection cyanogen root and application |
| CN109187455A (en) * | 2018-08-13 | 2019-01-11 | 天津理工大学 | It is a kind of detect sulphite in foods content kit and its application |
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| CN103502253A (en) * | 2011-03-01 | 2014-01-08 | 新加坡科技研究局 | Novel compounds with photoluminescnce properties and applications thereof |
| CN104262287A (en) * | 2014-09-02 | 2015-01-07 | 苏州罗兰生物科技有限公司 | Preparation and application of sulfite ratiometric fluorescent probe |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103502253A (en) * | 2011-03-01 | 2014-01-08 | 新加坡科技研究局 | Novel compounds with photoluminescnce properties and applications thereof |
| CN104262287A (en) * | 2014-09-02 | 2015-01-07 | 苏州罗兰生物科技有限公司 | Preparation and application of sulfite ratiometric fluorescent probe |
Non-Patent Citations (2)
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| CHEN, JINPING ET AL.: "Functionalization of boron dipyrrin (BODIPY) dyes through iridium and rhodium catalysis: A complementary approach to α- and β-substituted BODIPYs", 《CHEMISTRY - A EUROPEAN JOURNAL》 * |
| 于长江等: "氟硼荧染料修饰衍生研究进展", 《中国科技论文》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674183A (en) * | 2016-12-29 | 2017-05-17 | 济南大学 | Novel ratio type sulfite fluorescent probe as well as preparation method and biological application thereof |
| CN106674183B (en) * | 2016-12-29 | 2018-12-18 | 济南大学 | A kind of Ratio-type inferior sulfate radical fluorescence probe and preparation method thereof and biologic applications |
| CN109053778A (en) * | 2018-06-14 | 2018-12-21 | 忻州师范学院 | The reagent and its synthetic method of specific detection cyanogen root and application |
| CN109187455A (en) * | 2018-08-13 | 2019-01-11 | 天津理工大学 | It is a kind of detect sulphite in foods content kit and its application |
| CN109187455B (en) * | 2018-08-13 | 2021-10-15 | 天津理工大学 | Kit for detecting content of sulfite in food and application thereof |
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| Publication number | Publication date |
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| CN105820183B (en) | 2020-03-10 |
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