CN106700038A - Method for detecting gas signal molecule H2S through fluorescent probe - Google Patents

Method for detecting gas signal molecule H2S through fluorescent probe Download PDF

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CN106700038A
CN106700038A CN201611192609.9A CN201611192609A CN106700038A CN 106700038 A CN106700038 A CN 106700038A CN 201611192609 A CN201611192609 A CN 201611192609A CN 106700038 A CN106700038 A CN 106700038A
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CN106700038B (en
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曹达鹏
郭琳
王萌
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Beijing University of Chemical Technology
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    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract

The invention provides a method for detecting gas signal molecule H2S through a fluorescent probe and belongs to the field of fluorescent probe molecular detection. A proper organic ligand is selected, a covalent organic polymer probe material with the fluorescence property is prepared through a nickel-catalyzed Yamamoto coupling reaction, and H2S can be selectively sensed in the presence of other substances. The detection method is easy and convenient to operate, visual in signal, high in sensitivity and good in selectivity, and can achieve real-time in-situ detection.

Description

A kind of fluorescence probe detects gaseous signal molecule H2The method of S
Technical field
The present invention relates to one kind by covalent organic polymer material fluorescence sense detection signal molecule H2The new method of S, category In fluorescent probe molecule detection field.
Background technology
In recent years, research shows hydrogen sulfide (H2S) molecule is endogenous the third after carbon monoxide and nitric oxide Property gaseous signal molecule, with complicated BA, in clinical research and treatment use, receive increasing pass Note.Endogenic hydrogen sulfide is mainly amino acid (such as cysteine Cys and its derivative) by sulfur-bearing in cystathionie-β-synthesize Enzyme (cystathionine- β-synthase, CBS), 3-Mercaptopyruvate sulfurtransferase and cystathionie-γ-lyases Produced under the catalytic action of (cystathionine- γ-lyase, CSE).Appropriate hydrogen sulfide can not only adjust neural thin Born of the same parents and neuroendocrine, additionally it is possible to vascular smooth muscle, and protection stomach lining is played, reduce the effect of colonic pressure.But, mistake Amount hydrogen sulfide can produce multiple organs such as harm, influence central nervous system, respiratory system, and heart, brain to body, seriously When will cause various diseases, such as senile dementia, Down's syndrome, diabetes, cirrhosis etc..Therefore, hydrogen sulfide pair is detected Clinical research and treatment use etc. have important physiological significance.
At present, the method for detection hydrogen sulfide has various, such as spectra methods, sub-methyl blue spectrum analysis, electrochemical process, Gas chromatography, colorimetric method, high performance liquid chromatography (HPLC), capillary electrophoresis, metal inducement sulphur sedimentation etc..Wherein have Method it is cumbersome, it is necessary to be pre-processed to the carrying out of sample；The then tester having is expensive, and popularization degree is low.Fluorescence point Analysis method is easy to operate, and signal is directly perceived, sensitivity is high, selectivity is good, real-time in-situ detection, therefore, obtain the great pass of people Note.
Covalent organic material (Covalent Organic Materials, COMs) in recent years because its specific surface area is big, The excellent properties such as porous and size adjustable, have obtained more next at aspects such as gas storage, catalytic reaction, gas separation and electromagnetism More concerns and application.Meanwhile, covalent organic material is because having superior photoluminescent property containing abundant conjugated structure.Altogether The report of valency organic material sensing detection metal ion, explosive and small-molecule substance etc. is more.Liu little Ming seminars report The COF-JLU3 of azine-connection can detect Cu with fluorescence selectivity2+(X.Liu.,et.al..Chem.Commun.,2016,52, 6613--6616)；Feng Shouhua seminars report a kind of porous organic polymer material POP-HT, and this material can utilize glimmering Optical quenching quantitative determination Fe3+, while again can be using Fluorescence Increasing detection dioxanes (S.Feng., et.al.ACS Appl.Mater.Interfaces 2016,8,24097-24103)；Banerjee et al. is by simple liquid phase stripping means Be made COF nanolayer materials (TpBDH and TfpBDH), for detect nitro explosive (Banerjee, et.al.Chem.Sci.,2015,6,3931–3939).Compared with COF materials, the covalent organic polymer of COM materials is belonged to Material (Covalent organic Polymer, COP) has good fluorescence containing more abundant π-pi-conjugated structure Matter, and its hydrothermal stability is high, can be used for fluoroscopic examination.Before, we organize and also reported some on fluorescence sense detection Article.2012, report three kinds of COP materials (COP-2, COP-3, COP-4) to China et al. and can be used to sensing detection Explosive and small-molecule substance (Macromol.Rapid Commun.2012,33,1184-1190).Sang Nannan etc. has synthesized two Kind of COP materials (COP-301 and COP-401), can efficiently sensing detection picric acid PA (Sang., et.al.J.Mater.Chem.A,2015,3,92–96).COP materials have stability high, porous and solvent stability Advantage, has very big application potential as fluorescent material, up to the present has no COP materials on detection H2The report of S.
The content of the invention
First technical problem to be solved by this invention is directed to above-mentioned present Research and provides a kind of with fluorescence COP materials.
Second technical problem to be solved by this invention is the H that this COP materials can be detected under free position2S。
3rd technical problem to be solved by this invention be find a kind of fluorescence COP materials can sensitiveness simultaneously again energy Enough selective enumeration method H2S。
The technical scheme that present invention solution above-mentioned technical problem is used is as follows：
The present invention provides a kind of preparation method of the covalent organic polymer material of fluorescence, comprises the following steps：
By catalyst pair-(1,5- cyclo-octadiene) nickel (Ni (cod)2) and 2,2 '-bipyridyl under the conditions of anhydrous and oxygen-free plus Enter N, in N '-dimethyl formamide (DMF), add 1,5- cyclo-octadiene, uniform stirring half an hour, then distinguish in solution Add part 2,6- dibromo pyridines (referred to as 2,6-DP) and 2,4,6- tri- (4- bromophenyls) -1,3,5-triazines (TBT), 60~150 6~24 hours are reacted at DEG C.Room temperature is cooled to, to hydrochloric acid is added dropwise in reacted mixed solution, by a series of Stirring, filter, washing, drying is that can obtain the covalent organic polymer COP-409 materials of fluorescence.
N is 5-50000.
Preferred catalyst pair-(1,5- cyclo-octadiene) nickel (Ni (cod)2), 2,2 '-bipyridyl, 1,5- cyclo-octadiene, 2,6- Dibromo pyridine (abbreviation 2,6-DP), the mol ratio of 2,4,6- tri- (4- bromophenyls) -1,3,5- triazines (TBT) are：(1-99):(1- 99)(1-80):(0.05-20):(0.05-20)。
Filtering uses vacuum apparatus；Washing solid portion uses chloroform, tetrahydrofuran and deionized water respectively Deng washing；Drying is to dry a period of time at 80~240 DEG C in vacuum drying chamber.
The application of the COP-409 materials that the present invention is obtained, selective enumeration method S is used for as probe material2-Or H2S.Its energy Enough selective enumeration method S in the presence of other anion2-(H2S is similarly detected in described solution or dispersion liquid To).
It is dispersed or dissolved in organic solvent by by the covalent organic polymer COP-409 materials of fluorescence, then will not be of the same race The anion sodium salt solution of class is added in COP-409 material dispersion liquids, uses fluorescence spectrophotometer measurement fluorescence spectrum, note Record the fluorescence intensity of fluorescence spectrum；The covalent organic polymer COP- of fluorescence is verified by fluorescence data and ultra violet lamp 409 materials are capable of the sensing detection S of selectivity2-Or H2S.It is preferred that the concentration of anion sodium salt is identical in final detection architecture.
By several different types of anion sodium salts, including containing S2-Material (such as NaHSO3,NaIO3,NaSCN, NaNO3,NaCl,NaBr,Na2SO4,NaF,Na3PO4,NaI,Na2CO3,Na2S etc.) it is dissolved in organic solvent, it is configured to anion Solution (concentration is preferably 0.1M).Meanwhile, configuration concentration for (0.1~0.5) mg/mL COP-409 materials organic dispersions or Organic solution.A certain amount of different anion solutions are separately added into COP-409 materials organic dispersions or organic solution Anion-COP material solutions are obtained, the concentration of anion is reached 1mM.
COP-409 materials fluorescence sense detects S2-Or H2The process of S molecules is：First, examined using sepectrophotofluorometer The fluorescence emission spectrum of blank sample COP-409- dispersion liquids or solution is surveyed, by constantly excitation-emission process, one is found Maximum excitation wavelength λ ex are the maximum position of fluorescence intensity, and detect anion-COP materials in this, as excitation wavelength；To treat After the anion solutions of detection are added in COP-409- dispersion liquids or solution fully dissolving, by anion-COP material dispersion liquids It is added in cuvette, anion is detected using sepectrophotofluorometer；Repeat the sepectrophotofluorometer for using every time It is consistent.
Preferably, 220~700V of voltage, slit width is 5mm to the test condition of sepectrophotofluorometer.
The covalent organic polymer probe material with photoluminescent property that the present invention is prepared, in the feelings that other materials are present H can be optionally sensed under condition2S and S2-.This detection method is easy to operate, and signal is directly perceived, sensitivity is high, selectivity is good, can Real-time in-situ is detected.
Brief description of the drawings
Fig. 1 is material C OP-409 emission spectrum in methyl alcohol and exciting light spectrogram in embodiment 1.
Fig. 2 is the fluorescence intensity contrast block diagram of material C OP-409 detection different anions in embodiment 1.
Fig. 3 is material C OP-409 detections S in embodiment 12-Fluorescence picture design sketch of the ion under uviol lamp.
Fig. 4 be embodiment 2 in material C OP-409 to S2-Selective enumeration method.
Fig. 5 be embodiment 2 in material C OP-409 to S2-The fluorescent effect figure of selective enumeration method, irradiates under uviol lamp.
Fig. 6 be embodiment 3 in material C OP-409 to S2-Vitro detection.
Specific embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.Experimental drug unless otherwise indicated, comes Commercial channel (Alfa Aesar, Sigma Aldrich, Chengdu Ace spy company) is come from, and is not purified further, wherein institute With 1,5- cyclo-octadiene GaH2Dry, the DMF after purification refers to the DMF after removing water deoxygenation；
Embodiment 1：
The first step：2,2 '-bipyridyl of double (1,5- cyclo-octadiene) nickel of 4.09mmol and 4.09mmol is added into round bottom In flask, 65ml DMF after purification are subsequently adding, add 1, the 5- cyclo-octadiene of 3.96mmol, mixture is stirred at 40 DEG C, Until being completely dissolved.The organic ligand 2,6-DP and 0.314mmol of 0.471mmol are added in purple solution obtained above TBT.10 hours are reacted at 80 DEG C.After solution is cooled to room temperature, a certain amount of dense salt is added dropwise in deep purple solution Acid, until solution is changed into greenish transparent solution.After a period of time, using vacuum apparatus filtering solution, three are used respectively Chloromethanes, tetrahydrofuran and deionized water washing, it is therefore an objective to wash unreacted part, catalyst and other materials etc. off.Most Afterwards, in the vacuum drying chamber at 200 DEG C, dry 24 hours, that is, obtain solid COP-409 powder.
Second step：Configuration concentration is the methyl alcohol dispersion liquid of the COP-409 materials of 2mg/10ml.By quality being total to for 0.02g Valency organic polymer COP-409 is scattered in the methyl alcohol of 100ml, ultrasound, until be uniformly dispersed, it is standby.Meanwhile, by variety classes Sodium salt (NaHSO3,NaIO3,NaSCN,NaNO3,NaCl,NaBr,Na2SO4,NaF,Na3PO4,NaI,Na2CO3,Na2S) it is dissolved in In methyl alcohol, the anion solutions that concentration is 0.1M are configured to, it is standby.Remarks：Na2S is dissolved in methyl alcohol and produces H2S, that is, detect S2-Deng It is same as H2The detection of S.
3rd step：A certain amount of anion solutions are added separately in the COP-409- methyl alcohol dispersion liquids of 3ml, are configured to Different COP-409- anion-methyl alcohol dispersion liquids, wherein anion solubility is maintained at 1mM concentration.It is standby, survey fluorescence.
4th step：The COP-409- methyl alcohol dispersion liquids that second step is prepared are put into cuvette, use fluorescence spectrophotometry Meter measures its fluorescence spectrum, is operated by repeating excitation-emission, determines its maximum excitation wavelength, and maximum emission wavelength.So Afterwards, COP-409- anion-methyl alcohol dispersion liquid that the 3rd step of measure is prepared respectively obtains fluorescence emission spectrum, records its fluorescence intensity Maximum.
The fluorescence excitation spectrum and emission spectrum of COP-409- methyl alcohol are as shown in Figure 1.In fluorescence spectra, can be obvious Observe that material C OP-409 maximum excitation wavelength in methyl alcohol is 372nm, maximum emission wavelength is located at 432nm.Different The fluorescence intensity contrast block diagram of COP-409- anion-methyl alcohol is as shown in Figure 2.Other anion, fluorescence are added in COP-409 Intensity is substantially unchanged or varies less, as addition S2-Afterwards, fluorescence intensity has an obvious reduction, there occurs that fluorescence is sudden Go out.COP-409 adds S2-The front and rear fluorescent effect figure under uviol lamp is as shown in Figure 3.As can be seen that adding S2-Afterwards, COP- 409 fluorogram becomes very dark, and the intensity of light is very low, there is an obvious quenching.This explanation, this COP materials can be detected S2-, while also implying that COP-409 can detect H2S。
Embodiment 2：
Preparation method and experiment condition are basic with embodiment 1, and difference is the 3rd step, by several different anion It is added in COP materials simultaneously, then adds S2-, determine fluorescence spectra.It is illustrated in figure 4 in COP-409- methyl alcohol same When add same concentrations HSO3 -,IO3 -,SCN-,NO3 -,Cl-,Br-,SO4 2-,F-,PO4 3-,I-,CO3 2-Fluorescence spectrum afterwards and S is added on this basis2-Fluorescence spectrum comparison diagram afterwards.Fig. 5 is the fluorescent effect picture under uviol lamp, can substantially be seen Go out, even if in the presence of other anion, COP-409 also can significantly detect S2-, i.e. H2S。
Embodiment 3:
Preparation method and experiment condition are basic, and with embodiment 1, difference is second step, from cysteine (Cys), Glutathione (GSH) and Na2Used as tested substance, concentration is all 1mM to S, is detected using COP-409 as fluorescence probe.Such as Fig. 6 show, and COP-409 detects the fluorescence spectra of this several material.As can be seen that for relative Cys and GSH, COP-409 To H2S has a preferably selectivity quenching effect, being capable of selective enumeration method H2S。

Claims (10)

1. the preparation method of the covalent organic polymer material of a kind of fluorescence, it is characterised in that comprise the following steps：
By catalyst pair-(1,5- cyclo-octadiene) nickel (Ni (cod)2) and 2,2 '-bipyridyl N is added under the conditions of anhydrous and oxygen-free, In N '-dimethyl formamide (DMF), 1,5- cyclo-octadiene, uniform stirring half an hour, then to being separately added into solution are added Part 2,6- dibromo pyridines (referred to as 2,6-DP) and 2,4,6- tri- (4- bromophenyls) -1,3,5-triazines (TBT), at 60~150 DEG C 6~24 hours of reaction；Be cooled to room temperature, to being added dropwise over hydrochloric acid in reacted mixed solution, by a series of stirring, Filtering, wash, drying is that can obtain the covalent organic polymer COP-409 materials of fluorescence.
2. according to the method for claim 1, it is characterised in that
N is 5-50000.
3. according to the method for claim 1, it is characterised in that catalyst pair-(1,5- cyclo-octadiene) nickel (Ni (cod)2)、2,2’- Bipyridyl, 1,5- cyclo-octadiene, 2,6- dibromo pyridines (abbreviation 2,6-DP), 2,4,6- tri- (4- bromophenyls) -1,3,5- triazines (TBT) mol ratio is (1-99):(1-99)(1-80):(0.05-20):(0.05-20).
4. according to the method for claim 1, it is characterised in that filtering uses vacuum apparatus；Washing solid portion makes respectively Washed with chloroform, tetrahydrofuran and deionized water etc.；Drying is when drying one section in vacuum drying chamber 80~240 DEG C Between.
5. the covalent organic polymer material of fluorescence for being prepared according to claim 1-4 any one methods.
6. the application of the covalent organic polymer material of fluorescence for being prepared according to claim 1-4 any one methods, as spy Needle material is used for selective enumeration method S2-Or H2S。
7. according to the application of claim 6, it is characterised in that be dispersed or dissolved in by by the covalent organic polymer material of fluorescence In machine solvent, then different types of anion sodium salt solution is added in COP-409 material dispersion liquids, uses fluorescence spectrophotometer Photometer measurement fluorescence spectrum, records the fluorescence intensity of fluorescence spectrum；Verified by fluorescence data and ultra violet lamp The covalent organic polymer COP-409 materials of fluorescence are capable of the sensing detection S of selectivity2-Or H2S.It is preferred that cloudy in final detection architecture The concentration of ion sodium salt is identical.
8. one kind detects gaseous signal molecule H with fluorescence probe2The method of S, it is characterised in that use claim any one of 1-3 The covalent organic polymer material of fluorescence that method is prepared；By several different types of anion sodium salts including containing S2-'s Material, is dissolved in organic solvent, is configured to anion solutions；Meanwhile, configuration concentration is the COP-409 of (0.1~0.5) mg/mL Material organic dispersions or organic solution；A certain amount of different anion solutions are separately added into organic point of COP-409 materials Anion-COP material solutions are obtained in dispersion liquid or organic solution；COP-409 materials fluorescence sense detects S2-Or H2The mistake of S molecules Cheng Wei：First, the fluorescence emission spectrum of blank sample COP-409- dispersion liquids or solution is detected using sepectrophotofluorometer, is led to After constantly excitation-emission process, the maximum position of a maximum excitation wavelength λ ex i.e. fluorescence intensity is found, and in this, as Excitation wavelength detects anion-COP materials；Anion solutions to be detected are added in -409- dispersion liquids or solution fully After dissolving, anion-COP material dispersion liquids are added in cuvette, anion is detected using sepectrophotofluorometer；Every time Repeat the consistent of the sepectrophotofluorometer that uses.
9. according to the method for claim 8, it is characterised in that the test condition of sepectrophotofluorometer is preferred, voltage 220~ 700V, slit width is 5mm.
10. according to the method for claim 8, it is characterised in that anion solutions concentration is 0.1M；Anion-COP material solutions The concentration of middle anion reaches 1mM.
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CN109520984A (en) * 2018-12-06 2019-03-26 南通中国科学院海洋研究所海洋科学与技术研究发展中心 The rapid detection method of sulfate reducing bacteria in a kind of briny environment

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CN102146077A (en) * 2011-01-13 2011-08-10 上海大学 Fluoreneimidazole derivatives and preparation method thereof
CN104419401A (en) * 2013-08-28 2015-03-18 苏州罗兰生物科技有限公司 Fluorescent probe for detecting hydrogen sulfide by virtue of fluorescence enhancement as well as synthetic method and application of fluorescent probe

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CN1686976A (en) * 2005-03-17 2005-10-26 复旦大学 Conjugated ramification material of fluorine containing anthracene and pyrene at 9th position, preparation method and application
CN102146077A (en) * 2011-01-13 2011-08-10 上海大学 Fluoreneimidazole derivatives and preparation method thereof
CN104419401A (en) * 2013-08-28 2015-03-18 苏州罗兰生物科技有限公司 Fluorescent probe for detecting hydrogen sulfide by virtue of fluorescence enhancement as well as synthetic method and application of fluorescent probe

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Publication number Priority date Publication date Assignee Title
CN109280179A (en) * 2018-11-19 2019-01-29 天罡新材料（廊坊）股份有限公司 A kind of covalent organic framework material and preparation method thereof and the application in hindered amines synthesis
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CN109520984A (en) * 2018-12-06 2019-03-26 南通中国科学院海洋研究所海洋科学与技术研究发展中心 The rapid detection method of sulfate reducing bacteria in a kind of briny environment
CN109520984B (en) * 2018-12-06 2021-04-06 南通中国科学院海洋研究所海洋科学与技术研究发展中心 Method for rapidly detecting sulfate reducing bacteria in seawater environment

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