CN105733566A - Fluorescent probe used for sulfite or bisulphate and preparation method and application thereof - Google Patents
Fluorescent probe used for sulfite or bisulphate and preparation method and application thereof Download PDFInfo
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Abstract
A fluorescent probe used for sulfite or hydrosulphite is composed of benzindole quaternary ammonium salt, and the molecule has the following structure shown in the formula in the description, wherein R is respectively or simultaneously independent one of an alkyl group, an aryl group, a nitro group, an ester group and an ether group of 1-18 carbon elements or one of benzene, naphthalene, anthracene, pyrene, pyridine, pyrrole, indole, cooumarin, fluorescein, carbazole, rhodamine, fluorine and quinoline and a derivative; n is 0-20; X- is F- or Cl- or Br- or I- , and + is a positive charge. The fluorescent probe has the advantages that the fluorescent probe has good selectivity for sulfite, the linear relation, within the range of 0-8*10<-6>mol/L, between fluorescence intensity of fluorescent probe solution and the concentration of sulfite is good, and good actual practicability is shown; the fluorescent probe is short in response time and high in determining sensitivity and has a simple molecule structure, a synthesizing method is simple and convenient to implement, and therefore the fluorescent probe is quite easy to apply and popularize actually.
Description
Technical field
The present invention relates to high selectivity, the method for high-sensitivity detection sulfurous acid (hydrogen) salt, fluorescent probe that especially one class detects and preparation method and application for sulfurous acid (hydrogen) salt.
Background technology
In recent years, along with the raising of people's living standard, food-safety problem is the most increasingly paid close attention to by people.Food additive is the main cause causing food problems, and in numerous food additive, sulphite is a kind of important food preservative freshness retaining agent.Owing to sulphite has reproducibility, it is possible to prevent oxidase to the destruction of food nutrient composition and color change, microbial reproduction can be suppressed, thus there is the effects such as bleaching, anticorrosion, antioxidation, both can be as the antisepsis antistaling agent of fruit and vegerable, it is also possible to as the inhibitor preventing food spoilage.
But, too much sulphite also has harm, and its toxicity is mainly manifested in the following aspects: the food additive of (1) sulfites uses excess, it will the nutrient substance in heavy damage food, reduces nutritive value of food；Sulphite can react with the material such as aminoacid, protein, moreover it is possible to is combined with multivitamin, particularly with vitamin B1There is irreversible necleophilic reaction, vitamin B can be caused1Crack, be cracked into other product, vitamin B1With regard to this by total loss；Additionally, sulphite also can promote cell to morph, the oxidation etc. of induction unsaturated fatty acid endangers.(2) mankind eat the sulphite of excess and there will be the untoward reaction such as headache, nauseating, dizzy and asthma.Evidence suggests, some people extremely sensitive to sulphite, when running into very low concentration of sulphite, bronchus can cause asthma exacerbation by significant shrinkage.(3) if Long term Animal eats the food containing sulphite, it may appear that the symptom that neuroinflammatory, bone marrow suppression etc. are bad, the growth of animal can be brought obstacle by this.
In view of these serious side effects of sulphite, can high selectivity, the fluorescent probe of high-sensitivity detection sulphite in the urgent need to development.
Optochemical sensor is the new subject developed rapidly in recent years, and its appearance and supermolecule advancement of science (molecule assembling, host-guest chemistry, hydrogen bond action, hydrophobic interaction, Photo-induced electron transfer process and Intramolecular electron transfer etc.) are closely related.Its development is also closely related with many science and technology field (biochemistry, clinical medicine, pharmaceutical chemistry and environmental science etc.).Due to above-mentioned various reasons, effectively promote the development of Optochemical sensor.Optochemical sensor, according to the difference of its signal detection, can be divided into fluorescence chemical sensor (Fluorescent Chemosensor)
With colorimetric chemical sensor (Colorimetric Chemosensor).Fluorescence chemical sensor (fluorescent probe) mainly relies on fluorescence signal to be detection means, generally has the change of the enhancing of fluorescence, cancellation or emission wavelength.Colorimetric chemical sensor is then by mean of the change of color, observes by the naked eye and just can detect, and actual application is convenient.For the design of fluorescence chemical sensor that alien species are detected and research, it it is the problem received significant attention in recent years.The detection process of fluorescent optical sensor is, by device acceptor part, (alien species are included cation, anion and neutral molecule) carry out selectivity receiving, it is then passed through different mechanism such as Photo-induced electron transfer (PET) or energy transfer (LMCT), metal ligand charge transfer (MLCT), Intramolecular electron transfer (ICT), intermolecular exciplex, there is the change of optical signalling, then provide device information change during receiving species by the signal report section of device.
Carrying out the interaction between molecular detection by the luminescence phenomenon of molecule and the change of absorption spectrum, its advantage may be summarized to be the following aspects: (1) is convenient and swift, has the highest sensitivity；(2) optical fiber technology can be utilized to realize single celled real-time detection；(3) if there being bigger change on absorption spectrum, the purpose of detection can in the case of without the help of any instrument, directly be reached by the change of color.Many molecular structure factors and its residing environmental factors can be adopted to control fluorescence radiation efficiency and the change of absorption spectrum.Therefore, as luminous in TICT, MLCT is luminous, LMCT is luminous, excimer and Exciplex emission and and the relevant optical physics such as heavy atoms effect, Photo-induced electron transfer, electron energy transfer and photochemical characteristics etc. be the most successfully used in the design of chemical sensor.
Fluorescence chemical sensor, due to features such as its selectivity are good, highly sensitive, response time is fast, is paid close attention to by the most widely at present in the detection of biomolecule.Present stage, also little to the fluorescent probe of detection sulphite, mainly two types: one is to utilize inferior sulfate radical to realize Fluorescence Increasing with C=N double bond or ester bond addition；Another kind is the purpose sloughed by levulinate and reach Fluorescence Increasing.But the signal intensity of these fluorescent probes is affected (such as pH, viscosity, temperature) by several factors, so being not used to detect food or the content of biological complex system sulfite salt.
2,3,3-trimethyl-1-alkylbenzene diindyl quaternary ammonium salt is the fluorogen of a kind of strong electron withdrawing properties, its fluorescence maximum emission wavelength is in 465nm, and there is higher fluorescence quantum efficiency (Φ=0.36 in ethanol), and 2 with the presence of labile methyl group, in the basic conditions easily and aromatic aldehyde generation condensation reaction.At present the sulfite chemical sensor of document report is little, and these sensor selectivity are poor, sensitivity is low, fluorescence emission wavelengths is short, it is impossible to avoid the interference of other material in food or biological complex system, it is possible to the actual fluorescent probe applied almost without.
Summary of the invention
It is an object of the invention to overcome the deficiency in the performance of the fluorescent probe detected in prior art and structure for sulphite, there is provided a class formation novelty, function admirable, be applicable to sulphite detection, the fluorescent probe (fluorescence chemical sensor) and preparation method and application for sulphite detection that is fluorogen parent with benzindole quaternary ammonium salt, the especially fluorescent probe of additive sulfite content in detection food；The synthetic method of the fluorescent probe of detection sulphite in foods content is provided；The purposes of the fluorescent probe of detection sulphite in foods content is provided.
Technical scheme:
One class, for the fluorescent probe of sulfurous acid (hydrogen) salt detection, is made up of benzindole quaternary ammonium salt, and its chemical molecular formula is C16+mH14+nN1+xOyX exists, and wherein m, n, x, y are the integer of 0-100, and molecule has a structure that
Wherein: the one in the alkyl for 1-18 carbon, aryl, nitro, ester group and ether the most independent for R, or the one in benzene, naphthalene, anthracene, pyrene, pyridine, pyrroles, indole, coumarin, fluorescein, carbazole, rhodamine, fluorenes and quinoline and derivant thereof；N is 0-20；X-For F-、Cl-、Br-Or I-,+for positive charge.
The synthetic method of the fluorescent probe detected for sulfurous acid (hydrogen) salt described in one class, step is as follows:
Being dissolved in organic solvent by aldehyde with substituent R, add haloalkyl benzindole quaternary ammonium salt under with or without catalysts conditions, haloalkyl benzindole quaternary ammonium salt is 0.5-100 with the molar ratio of the aldehyde with substituent R；React 0.5-60 hour at reaction temperature is 25-120 DEG C；Then solution is concentrated, utilize silica gel column chromatography to obtain target compound.
One in the alkyl for 1-18 carbon, aryl, nitro, ester group and ether that substituent R in the described aldehyde with substituent R is the most independent, or the one in benzene, naphthalene, anthracene, pyrene, pyridine, pyrroles, indole, coumarin, fluorescein, carbazole, rhodamine, fluorenes and quinoline and derivant thereof；And substituent R is directly on the adjacent carbon atom of aldehyde.
Alkyl in described haloalkyl benzindole quaternary ammonium salt is the alkyl chain containing 1-12 carbon or the one of the benzene of 1-8 carbon, naphthalene, anthracene, pyrene, pyridine, pyrroles, indole and coumarin and derivant thereof, and the alkyl of 1-10 carbon therein is optionally substituted by halogen；Halogen is F-、Cl-、Br-Or I-。
Described organic solvent is the mixture of one or more arbitrary proportions in methanol, ethanol, dimethylformamide, dimethyl acetylamide, dimethyl sulfoxide, acetonitrile, dioxane, dichloromethane, benzene and toluene.
Described catalyst is pyridine, hexahydropyridine, triethylamine or potassium carbonate.
A kind of application of the fluorescent probe of described detection sulphite in foods content, blood, serum or the detection of tissue sulfite (hydrogen) salt in the detection of food safety sulfite (hydrogen) salinity and the detection of chemical simulation living things system sulfite (hydrogen) salt and clinical medicine.The concrete practice is: be dissolved in by probe molecule in the buffer solution of normal saline or phosphate (PBS), or probe molecule is dissolved in methanol, ethanol, acetonitrile, dimethyl sulfoxide or diformamide organic solvent, or being dissolved in by probe molecule in the mixed solvent of water and above-mentioned organic solvent arbitrary proportion, being finally configured to concentration is 1 × 10-5The probe solution of mol/L；Then adding concentration in the above-mentioned probe solution be dissolved with probe molecule is the sample solution containing sulfurous acid (hydrogen) salt, and sample solution is 10 microlitres with the amount ratio of probe solution: 1 milliliter.
The invention have the advantage that this fluorescent probe has good selectivity to sulfurous acid (hydrogen) salt, detection is not interfered with by other additives in food such as citric acid, cyclamate, saccharin sodium, dibenzylatiooluene, nitrate, enzyme inhibitor etc.；The fluorescence intensity of this fluorescent probe solution and the concentration of sulphite are in 0-8 × 10-6Linear relationship in the range of mol/L is good, shows good practical application；Fluorescent probe response time is short for this, it is highly sensitive to measure, molecular structure simple, simple synthetic method so that its actual popularization and application.
Accompanying drawing explanation
Fig. 1 is the one-dimensional hydrogen nuclear magnetic spectrogram of the fluorescent probe in embodiment 1, and abscissa is chemical shift, and vertical coordinate is signal intensity.
Fig. 2 is the selectivity to sulfurous acid (hydrogen) salt of the fluorescent probe in embodiment 1, and abscissa is different ions, and vertical coordinate is fluorescence intensity ratio.
Fig. 3 is the picture to food-sucrose sulfite salt detection of the fluorescent probe in embodiment 2.
Fig. 4 is fluorescence intensity and the linear dependence of bisulfite salinity of the fluorescent probe in embodiment 3, and abscissa is the concentration of bisulfites, and vertical coordinate is fluorescence intensity ratio.
Fig. 5 is that the fluorescent probe in embodiment 4 is in the intracellular response to bisulfites.
Detailed description of the invention
Embodiment 1:
A kind of fluorescent probe for the detection of sulfurous acid (hydrogen) salt, chemical formula is C29H29N2F4I, and molecule has a structure that
Preparation method step is as follows:
Benzindole quaternary ammonium salt 1 mM is dissolved in 20 milliliters of dehydrated alcohol, being subsequently adding 1.2 mMs of pentafluorobenzaldehyde, add 20 microlitre hexahydropyridines as catalyst, 45 DEG C are reacted 4 hours, after being concentrated by reaction solution, obtain dark red solid compound fluorescent probe A through silica gel column chromatography.
1H NMR(400MHz,d6-DMSO): δ (ppm)=8.45 (d, 1H), 8.33 (d, 1H), 8.24 (d, 1H), 8.19 (d, 1H), 8.07 (d, 1H), 7.82 (t, 1H), 7.75 (t, 1H), 7.51 (d, 1H), 4.75 (q, 2H), 3.41 (s, 4H), 2.00 (s, 6H), 1.65 (s, 6H), 1.54 (t, 3H).13C NMR(100MHz,d6-DMSO):δ(ppm)182.0,139.5,138.6,137.0,133.9,
131.8,130.5,129.0,128.0,127.2,123.7,115.6,113.8,54.4,52.2.52.2,43.58,26.6,25.8,23.8,14.16.
Fig. 1 is the one-dimensional hydrogen nuclear magnetic spectrogram of the fluorescent probe in embodiment 1, and abscissa is chemical shift, and vertical coordinate is signal intensity.
The evaluation fluorescent probe A selectivity to sulphite:
Fig. 2 is that fluorescent probe A is dissolved in glycerol/phosphate (PBS) buffer solution (volume ratio is 2:3), and obtaining concentration is 1.0 × 10-5The fluorescent probe solution A of mol/L, adds the change of solution fluorescence intensity when being the various anion of 10 times of moles of compound.Fluorescent probe excitation wavelength is 322nm, a length of 467nm of transmitted wave.When adding sulfurous acid (hydrogen) salt of 1 times of mole in fluorescent probe solution A, the fluorescence intensity of this fluorescent probe solution strengthens nearly 100 times.And when adding the various anion of 10 times of moles, the fluorescence intensity of this fluorescent probe solution, almost without significant change, illustrates that this fluorescent probe has good Selective recognition and practical application to sulphite.
Embodiment 2:
A kind of fluorescent probe for the detection of sulfurous acid (hydrogen) salt, chemical formula is C29H29N2F4I, and molecule has a structure that
Preparation method step is as follows:
Benzindole quaternary ammonium salt 1 mM is dissolved in 20 milliliters of dehydrated alcohol and toluene mixed solution (volume ratio is 1:1), it is subsequently adding 10 mMs of pentafluorobenzaldehyde, add 40 microlitre hexahydropyridines as catalyst, 25 DEG C are reacted 10 hours, after being concentrated by reaction solution, obtain dark red solid compound fluorescent probe A through silica gel column chromatography.
1H NMR(400MHz,d6-DMSO): δ (ppm)=8.45 (d, 1H), 8.33 (d, 1H), 8.24 (d, 1H), 8.19 (d, 1H), 8.07 (d, 1H), 7.82 (t, 1H), 7.75 (t, 1H), 7.51 (d, 1H), 4.75 (q, 2H), 3.41 (s, 4H), 2.00 (s, 6H), 1.65 (s, 6H), 1.54 (t, 3H).13C NMR(100MHz,d6-DMSO):δ(ppm)182.0,139.5,138.6,137.0,133.9,131.8,130.5,129.0,128.0,127.2,123.7,115.6,113.8,54.4,52.2.52.2,43.58,26.6,25.8,23.8,14.16.
Evaluate this fluorescent probe A food (sucrose) sulfite salt is detected:
Fig. 3 is 1.0 × 10-5The mixed solution (volume ratio is 3:2) of mol/L fluorescent probe water and ethanol adds 1.0 × 10-5Change in fluorescence after mol/L aqueous sucrose solution, result shows: compound A is capable of detecting when the sulphite in food, and demonstrates that obvious color changes, and shows good practical application.
Embodiment 3:
A kind of fluorescent probe for the detection of sulfurous acid (hydrogen) salt, chemical formula is C31H33N2O2I, and molecule has a structure that
Preparation method step is as follows:
Being dissolved in 15 milliliters of anhydrous acetonitriles by benzindole quaternary ammonium salt 1 mM, be subsequently adding 2 mMs of coumarin aldehyde, be not added with catalyst, 80 DEG C are reacted 4 hours, after being concentrated by reaction solution, obtain violet solid compound fluorescent probe B through silica gel column chromatography.
1H NMR(400MHz,CDCl3): δ 7.96 (m, 1H), 7.86 (dd, 1H), 7.77 (dd, 1H), 7.59 (m, 1H), 7.53 7.42 (m, 2H), 7.17 (dd, 1H), 6.84 (d, 1H), 6.61 (dd, 1H), 6.43 (d, J=2.1Hz, 1H), 6.25 (d, 1H), 6.09 (d, 1H), 3.34 (m, 4H), 1.42 (s, 6H), 1.43 1.36 (m, 2H), 1.30 1.23 (m, 3H), 1.10 (t, 6H).13C NMR(100MHz,CDCl3):δ173.95,161.82,160.32,154.63,141.97,141.00,139.69,139.07,133.09,131.21,129.70,129.57,129.20,128.37,128.19,124.42,119.32,113.99,113.64,110.71,109.17,97.39,52.74,44.92,41.95,27.42,14.81,12.29.
The fluorescence intensity of fluorescent probe B and the detection of the linear dependence of sulfite concentration:
Fig. 4 is the change curve with sulfite concentration of the fluorescence intensity ratio at transmitted wave a length of 465 and 592nm, and result shows: (concentration is 1.0 × 10 to compound B solution-5Mol/L) the concentration of fluorescence intensity and sulphite in 0-8 × 10-6In the range of linear dependence good, show good practical application.
Embodiment 4:
A kind of fluorescent probe for the detection of sulfurous acid (hydrogen) salt, chemical formula is C23H23N2I, and molecule has a structure that
Preparation method step is as follows:
Benzindole quaternary ammonium salt 1 mM is dissolved in 30 milliliters of anhydrous dimethyl formamides, it is subsequently adding 2 mMs of 4-pyridine carboxaldehydes, add 20 microlitre triethylamines as catalyst, 100 DEG C are reacted 2 hours, after being concentrated by reaction solution, obtain yellow solid compound fluorescent probe C through silica gel column chromatography.
1H NMR(400MHz,CDCl3):δ8.53(dd,1H),7.91(m,1H),7.80(dd,1H),7.72(dd,1H),7.66(m,1H),7.59(m,1H),7.51–7.40(m,3H),7.29(m,1H),5.88(d,1H),5.27(d,1H),1.41(s,6H),1.44–1.36(m,1H),1.35–1.28(m,3H).13C NMR(100MHz,CDCl3):δ173.55,155.32,149.40,141.79,141.00,139.69,136.49,133.09,129.70,129.57,129.20,128.37,128.19,124.42,122.88,122.23,113.64,103.57,52.74,41.95,27.42,14.81.
Evaluate fluorescent probe C in the intracellular response to bisulfites.Fig. 5 is the contrast of change in fluorescence before and after addition sodium sulfite in cell culture fluid, and result shows: compound C can present preferable fluorescence intensity in cell, shows good practical application.
Embodiment 5:
A kind of fluorescent probe for the detection of sulfurous acid (hydrogen) salt, chemical formula is C36H38N2I2, and molecule has a structure that
Preparation method step is as follows:
Benzindole quaternary ammonium salt 2 mMs is dissolved in 20 milliliters of dehydrated alcohol, being subsequently adding 1 mM of terephthalaldehyde, add 20 microlitre pyridines as catalyst, 60 DEG C are reacted 15 hours, after being concentrated by reaction solution, obtain violet solid compound fluorescent probe D through silica gel column chromatography.
1H NMR(400MHz,CDCl3):δ9.84(d,1H),7.93(m,1H),7.82(dd,1H),7.72(m,3H),7.59(m,1H),7.52–7.41(m,2H),7.41–7.35(m,2H),5.76(s,2H),1.42(s,6H),1.45–1.36(m,2H),1.36–1.28(m,3H). 13C NMR(100MHz,CDCl3)δ192.07,173.55,146.66,141.00,139.69,136.30,135.40,133.09,130.19,129.70,129.57,129.20,128.37,128.19,127.25,124.42,113.64,101.91,52.74,41.95,27.42,14.81。
Claims (7)
1. a class is for the fluorescent probe of sulfurous acid (hydrogen) salt detection, it is characterised in that by benzindole quaternary ammonium salt
Constituting, its chemical molecular formula is C16+mH14+nN1+xOyX, wherein m, n, x, y are the integer of 0-100,
And molecule has a structure that
Wherein: the alkyl for 1-18 carbon, aryl, nitro, ester group and ether the most independent for R
One in base, or benzene, naphthalene, anthracene, pyrene, pyridine, pyrroles, indole, coumarin, fluorescein, carbazole,
One in rhodamine, fluorenes and quinoline and derivant thereof；N is 0-20；X-For F-、Cl-、Br-Or I-,+
For positive charge.
2. the synthetic method of the fluorescent probe that a class detects for sulfurous acid (hydrogen) salt as claimed in claim 1,
It is characterized in that step is as follows:
Aldehyde with substituent R is dissolved in organic solvent, under with or without catalysts conditions, adds alkyl halide
Base benzindole quaternary ammonium salt, haloalkyl benzindole quaternary ammonium salt with the molar ratio of the aldehyde with substituent R is
0.5-100；React 0.5-60 hour at reaction temperature is 25-120 DEG C；Then solution is concentrated, utilize
Silica gel column chromatography obtains target compound.
The synthetic method of the fluorescent probe detected for sulfurous acid (hydrogen) salt the most according to claim 2, its
Be characterised by: substituent R in the described aldehyde with substituent R the most independent for 1-18
One in the alkyl of carbon, aryl, nitro, ester group and ether, or benzene, naphthalene, anthracene, pyrene, pyridine, pyrrole
Cough up, one in indole, coumarin, fluorescein, carbazole, rhodamine, fluorenes and quinoline and derivant thereof；And
And substituent R is directly on the adjacent carbon atom of aldehyde.
The synthetic method of the fluorescent probe detected for sulfurous acid (hydrogen) salt the most according to claim 2, its
Be characterised by: the alkyl in described haloalkyl benzindole quaternary ammonium salt be the alkyl chain containing 1-12 carbon or
The one of the benzene of 1-8 carbon, naphthalene, anthracene, pyrene, pyridine, pyrroles, indole and coumarin and derivant thereof, its
In the alkyl of 1-10 carbon be optionally substituted by halogen；Halogen is F-、Cl-、Br-Or I-。
The synthetic method of the fluorescent probe detected for sulfurous acid (hydrogen) salt the most according to claim 2, its
It is characterised by: described organic solvent is methanol, ethanol, dimethylformamide, dimethyl acetylamide, diformazan Asia
The mixing of one or more arbitrary proportions in sulfone, acetonitrile, dioxane, dichloromethane, benzene and toluene
Thing.
The synthetic method of the fluorescent probe detected for sulfurous acid (hydrogen) salt the most according to claim 2, its
It is characterised by: described catalyst is pyridine, hexahydropyridine, triethylamine or potassium carbonate.
7. an application for the fluorescent probe of detection sulphite in foods content as claimed in claim 1, it is special
Levy and be: for detection and the chemical simulation living things system Central Asia of food safety sulfite (hydrogen) salinity
Blood, serum or the detection of tissue sulfite (hydrogen) salt in the detection of sulphuric acid (hydrogen) salt and clinical medicine.
The concrete practice is: be dissolved in by probe molecule in the buffer solution of normal saline or phosphate (PBS), or
Probe molecule is dissolved in methanol, ethanol, acetonitrile, dimethyl sulfoxide or diformamide organic solvent, or will
Probe molecule is dissolved in the mixed solvent of water and above-mentioned organic solvent arbitrary proportion, is finally configured to concentration and is
1×10-5The probe solution of mol/L；Then in the above-mentioned probe solution be dissolved with probe molecule, add concentration
For the sample solution containing sulfurous acid (hydrogen) salt, sample solution is 10 microlitres with the amount ratio of probe solution: 1 milli
Rise.
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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 |
| CN106674195A (en) * | 2016-12-26 | 2017-05-17 | 安徽大学 | Benzoindole derivative two-photon fluorescent probe and preparation method and application thereof |
| CN108623575A (en) * | 2017-03-21 | 2018-10-09 | 泰山医学院 | A kind of fluorescence probe that is simple and effectively detecting sulphite |
| 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 |
| CN109438425A (en) * | 2018-10-10 | 2019-03-08 | 复旦大学 | A kind of near infrared fluorescent dye, preparation method and application |
| CN109575000A (en) * | 2019-01-02 | 2019-04-05 | 济南大学 | A kind of turn-on type sulfur dioxide fluorescence probe and its preparation method and application |
| CN110563708A (en) * | 2019-09-18 | 2019-12-13 | 天津理工大学 | Turn-on type fluorescent probe for rapidly detecting sulfite (hydrogen) and synthesis method and application thereof |
| CN111040465A (en) * | 2019-12-17 | 2020-04-21 | 中国科学院合肥物质科学研究院 | Near-infrared fluorescent probe for bimodal detection of sulfur dioxide and preparation method and application thereof |
| CN112538037A (en) * | 2020-10-28 | 2021-03-23 | 福建师范大学 | Active inorganic sulfur species two-photon fluorescent probe and synthetic method and application thereof |
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| CN108623575A (en) * | 2017-03-21 | 2018-10-09 | 泰山医学院 | A kind of fluorescence probe that is simple and effectively detecting sulphite |
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| 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 |
| 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 |
| CN109438425A (en) * | 2018-10-10 | 2019-03-08 | 复旦大学 | A kind of near infrared fluorescent dye, preparation method and application |
| CN109438425B (en) * | 2018-10-10 | 2022-03-01 | 复旦大学 | Near-infrared fluorescent dye, and preparation method and application thereof |
| CN109575000A (en) * | 2019-01-02 | 2019-04-05 | 济南大学 | A kind of turn-on type sulfur dioxide fluorescence probe and its preparation method and application |
| CN110563708A (en) * | 2019-09-18 | 2019-12-13 | 天津理工大学 | Turn-on type fluorescent probe for rapidly detecting sulfite (hydrogen) and synthesis method and application thereof |
| CN110563708B (en) * | 2019-09-18 | 2023-01-24 | 天津理工大学 | Turn-on type fluorescent probe for rapidly detecting sulfite (hydrogen) salt, and synthesis method and application thereof |
| CN111040465A (en) * | 2019-12-17 | 2020-04-21 | 中国科学院合肥物质科学研究院 | Near-infrared fluorescent probe for bimodal detection of sulfur dioxide and preparation method and application thereof |
| CN112538037A (en) * | 2020-10-28 | 2021-03-23 | 福建师范大学 | Active inorganic sulfur species two-photon fluorescent probe and synthetic method and application thereof |
| CN114507212A (en) * | 2022-02-25 | 2022-05-17 | 河南理工大学 | Benzoindoline-dihydroquinolinone derivative fluorescent probe and preparation method and application thereof |
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