CN106995419A - Fluorescence probe with aggregation-induced emission property and its production and use - Google Patents

Fluorescence probe with aggregation-induced emission property and its production and use Download PDF

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CN106995419A
CN106995419A CN201610049647.2A CN201610049647A CN106995419A CN 106995419 A CN106995419 A CN 106995419A CN 201610049647 A CN201610049647 A CN 201610049647A CN 106995419 A CN106995419 A CN 106995419A
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alkyl
compound
formula
bacterium
anion surfactant
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CN106995419B (en
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唐本忠
高蒙
秦安军
王罗超
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • G01—MEASURING; TESTING
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    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • 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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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur

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Abstract

The present invention relates to a kind of formula I fluorescence probes with aggregation-induced emission (AIE) property and preparation method thereof, wherein, R1, R2It is independently hydrogen, C1-18Alkyl, halogen, C1-18Alkyl oxy, C1-18Alkyl sulfenyl, aryl, heteroaryl；R3, R4, R5For C1-30Alkyl；R6For straight key, C1-6Alkylidene；A-For anion.The fluorescence probe, which can be realized by being formed in situ zwitterion aggregation, lights detection anion surfactant, and it has high selectivity and high sensitivity to anion surfactant.In addition, the fluorescence probe can be also used for the fluorescent staining of bacterium, have the advantages that background noise is low, staining efficiency is high, need not additionally wash.

Description

Fluorescence probe with aggregation-induced emission property and its production and use
Technical field
The invention belongs to surfactant detection field, more particularly to a kind of detection of anion surfactant Method.
Background technology
Anion surfactant, especially alkylsulfonate are most important surfactant and quilt in commodity A large amount of productions, such as：Neopelex (SDBS), NaLS (SLS), dodecyl Sodium sulphate (SDS) etc..They cleaning, agricultural, cosmetics and medical industry be widely used as detergent, Emulsifying agent, foaming agent and dispersant.Due to being widely used for they, its residue in water body is to ecology Environment is likely to result in serious harm, such as：Suppress aquatic organism activity, accelerate the diffusion of oily pollutant.In addition, Anion surfactant may cause to stimulate and cause inflammation to human eye and skin.In order that anionic surface The detection of activating agent is even at home or remote districts can also implement, it is also very desirable to development it is a kind of it is simple to operate, Effective detection method with low cost.At present, in the literature, it has been reported that substantial amounts of to be used to detect the moon The method of ionic surface active agent, such as GC/LC-MS, colorimetric method, potentiometry, immunoassay, Capillary Electrophoresis and flow injection analysis.However, these methods also have following shortcoming, such as：Need Large-scale retainer instrument, it is cumbersome, using poisonous chlorinated solvent and be difficult to in-situ study.
In recent years, Fluorometric assay anion surfactant shows significant advantage, such as：Sensitivity Cost high, simple to operate is low.However, the fluorescent material with aggregation inducing fluorescent quenching (ACQ) property Under state of aggregation, easily occur the self-quenching of fluorescence, and its own also can in the high background fluorescence of solution state Substantially reduce the signal to noise ratio in detection process.
With aggregation inducing fluorescent quenching (ACQ) on the contrary, glimmering with aggregation-induced emission (AIE) property Light probe, lights very weak in weak solution, but luminous very strong in state of aggregation.By forming luminous aggregation, AIE probes have been widely used for detection metal ion, enzyme, DNA etc..In addition, AIE molecules are also used for Detect critical micelle concentration, the insoluble drug release of monitoring micella parcel, the form of micella is monitored using fluorescence imaging The processes such as transformation.
The content of the invention：
It is an object of the invention to provide a kind of fluorescence probe with aggregation-induced emission (AIE) property, it can For detection anion surfactant.
It is yet another object of the invention to provide the preparation method of above-mentioned fluorescence probe with and application thereof.
The object of the invention is realized based on following technical scheme：
A kind of compound shown in Formulas I：
Wherein：
R1, R2It is independently hydrogen, C1-18Alkyl, halogen, C1-18Alkyl oxy, C1-18Alkyl sulfenyl, virtue Base, heteroaryl；R3, R4, R5It is independently C1-30Alkyl；R6For straight key, C1-6Alkylidene；A-For the moon Ion.
Described alkyl can be straight or branched alkyl；For example, methyl, ethyl, propyl group, butyl, isobutyl Base, tert-butyl group etc..
Described aryl refers to the monocyclic or polycyclic aromatic group with 6-20 carbon atom, representational aryl bag Include：Phenyl, naphthyl, anthryl, pyrenyl etc..
Described heteroaryl refer to 1-20 carbon atom, 1-4 selected from N, S, O it is heteroatomic monocyclic or Polycyclic hetero-aromatic group, representational heteroaryl includes：Pyrrole radicals, pyridine radicals, pyrimidine radicals, imidazole radicals, Thiazolyl, indyl, azepine naphthyl, azepine anthryl, azepine pyrenyl etc..
In one embodiment, R1, R2It is independently hydrogen, C1-6Alkyl, halogen, C1-6Alkyl oxy, C1-6Alkyl sulfenyl.
In another embodiment, R3, R4, R5In at least one be C8-30Alkyl, more preferably C10-24 Alkyl, and preferably C12-22Alkyl, or C14-20Alkyl.
In further embodiment, R3, R4, R5In a group be chain alkyl, and another two base Group is short-chain alkyl, for example, R3, R4, R5In a group be C8-30Alkyl, more preferably C10-24 Alkyl, and preferably C12-22Alkyl, or C14-20Alkyl；And another two group is independently C1-8Alkyl, More preferably C1-6Alkyl.
In further embodiment, R6For straight key ,-CH2-、-CH2CH2-、-CH2CH2CH2-。
It is preferred that, the anion be halogen ion, perchlorate, sulfate ion, nitrate ion, Hexafluorophosphoricacid acid ions etc..The halogen ion is preferably chlorion.
It is preferred that, the formula I is below formula (Ia)：
Wherein, R1、R2、R3、R4、R5、A-It is as defined above.
It is preferred that, in Formulas I a, R1For hydrogen, R2For hydrogen, R3, R4For methyl, R5For octadecyl, A- For anion.
It is further preferred that compound of formula I is selected from：
N- (3- (benzo [d] thiazol-2-yl) -4- hydroxybenzyls)-N, N- dimethyl stearyl -1- ammonium chlorides；
Present invention also offers a kind of preparation method of above-mentioned compound of formula I, including by Formula II compound and formula III compounds are under the oxidation of Protic Acid Catalyzed and oxidising agent, and reaction obtains compound of formula I：
Wherein, R1、R2、R3、R4、R5、R6、A-It is as defined above.
It is preferred that, the Bronsted acid is concentrated hydrochloric acid, and the oxidising agent is hydrogen peroxide.
The Formula II compound can be obtained by following preparation method, including：By formula IV compound and Formula V Compound reaction obtains Formula II compound.
Wherein, R2、R3、R4、R5、R6、A-It is as defined above.
Compound of formula I of the present invention has aggregation-induced emission (AIE) property.The structure includes 2- (2'- hydroxy phenyls) benzothiazole (HBT) molecular skeleton, it has the hexa-atomic ring hydrogen bond of intramolecular and connection benzo C-N the singly-bounds of thiazole unit and substituted benzene unit.Due to its excitation state proton intramolecular transfer process (ESIPT) Property, launches with alcohol of formula and keto-acid, respectively with normal stoke shift and very big stoke shift (being more than 150nm).Because intramolecular hydrogen bond is easily destroyed by polar solvent, the hair of alcohol of formula and keto-acid Penetrate the polarity height correlation of ratio and molecule local environment.In polar solvent, the compound is showed only as Alcohol of formula lights.And in state of aggregation, meeting close-packed arrays between molecular structure suppress intramolecular C-N singly-bounds Rotation, and intramolecular hydrogen bond can be protected from the interference of external environment.Due to the fluorescent emission of the compound The state of aggregation of polarity and molecule to environment is very sensitive, therefore they are particularly suitable as surfactant Sensing material.
Relative to single cation or anionic surfactant system, even in far below respective critical glue In the case of beam concentration, the mixed system of the surfactant with opposite charges also tends to shape in the solution Into zwitterion aggregation or micella, this is due to electrostatic and hydrophobic synergy can effectively reduce surface What power was caused.The present invention based on AIE dyestuffs state of aggregation High Efficiency Luminescence characteristic, using with AIE properties Positively charged amphipathic probe molecule (compound of formula I), by be formed in situ zwitterion aggregation or Micella detects anion surfactant.Pass through the intermolecular close-packed arrays in aggregation, HBT skeletons Internal molecular motion limited and intramolecular hydrogen bond is secured against environmental disturbances (see Fig. 1).
And then, present invention also offers purposes of the compound of formula I in detection anion surfactant.
According to the present invention, described anion surfactant can for carboxylate, sulfuric acid, sulfonate and Phosphate ester salt.It is preferred that, described anion surfactant is the anionic surface for being connected with sulfonic acid group Activating agent, such as neopelex (SDBS), lauryl sodium sulfate (SDS) etc..
Compound of the present invention and anion surfactant formation zwitterion aggregation.It is molten in polarity In agent, when the concentration of compound of the present invention and the zwitterion micella of anion surfactant formation is high When its critical micelle concentration, compound of the present invention can form zwitterion with anion surfactant Micella.So that the microenvironment polarity residing for compound of the present invention diminishes.So as to protect the chemical combination The hydrogen bond of thing intramolecular.The critical concentration of zwitterion micella is substantially less than anion in described mixed system The critical micelle concentration of surfactant.
Compound of the present invention can be used for the forming process of monitoring zwitterion micella, with efficient and spirit Quick advantage.Compound of the present invention is less than for the test limit (3 δ/S) of anion surfactant 0.08 μM, far below the national standard based on sub-methyl blue spectrum analysis (test limit is about 0.14 μM).
In addition, being limited (RIM) based on excited state intramolecular proton transfer (ESIPT) and internal molecular motion Mechanism, when anionic surfactant concentration is relatively low, the light emission ratio of keto-acid/enol form of compound of formula I Concentration with anion surfactant is linear, therefore, it can keto-acid/alkene by compound of formula I The light emission ratio of alcohol of formula quantitatively determines the concentration of surfactant in water.
Present invention also offers a kind of method for detecting anion surfactant, including, in anionic surface Compound of formula I of the present invention is added in the solution of activating agent, in observed under fluorescent light or detection fluorescence spectrum.
Compound of the present invention has faint fluorescent emission in aqueous, but when itself and anion table Face activating agent can send very strong fluorescence after combining generation aggregation, and therefore, it may be used as excellent light Probe, realizes the disposable fluorescence imaging of the bacterium surrounded to negative electrical charge outer membrane.
Further, the invention provides compound of formula I the disposable fluorescent staining of bacterium purposes.
According to the present invention, described bacterium is the bacterium surrounded with negative electrical charge outer membrane, such as Escherichia coli, Hay bacillus, staphylococcus aureus etc..
Compound of formula I of the present invention can be used for direct staining bacterium without further washing step. And the toxicity of low-down directed toward bacteria is shown, is conducive to the fluorescent staining of its directed toward bacteria to test.
It is made up of due to the outer membrane of bacterium negatively charged amphipathic molecule, and Formulas I of the present invention Compound is the amphipathic molecule with positive charge, thus its can by electrostatic and hydrophobic effect with outside bacterium Film forms strong affinity；After in combination, athletic meeting is restricted in the rotation equimolecular of the compound, According to the mechanism of aggregation-induced emission, after internal molecular motion is limited, it lights and can be remarkably reinforced.And be dissolved in The compound not combined with bacterium in solution, due to internal molecular motion, causes luminous very weak.It can be seen that, Compound of the present invention sends out hyperfluorescence after being combined with bacterium, and it is faint to light in the solution, right in the height Than under degree, only observing the fluorescence signal on bacterium.And traditional fluorescent material, lighted very in weak solution By force, it is therefore desirable to centrifuge washing, the fluorescence molecule in weak solution is removed, be can be only used on observation bacterium Fluorescence signal.
The method that the present invention also provides a kind of disposable fluorescent staining of bacterium, including, by Formulas I of the present invention Compound is co-cultured with bacterium, and its fluorescence is directly observed without separation, such as micro- using laser-scanning confocal Mirror is observed.
The present invention at least has the advantages that：
1st, compound of the present invention is less than 0.8 for the test limit (3 δ/S) of anion surfactant μM, far below the national standard based on sub-methyl blue spectrum analysis, and do not need the toxic reagents such as chloroform Extraction, concentration, can be detected with direct in-situ, easy to operate.
2nd, compound of the present invention may be used as it is excellent light probe, bacterium can be carried out disposable glimmering Photoimaging, without separation.
3rd, compound of the present invention prepares simple.
Brief description of the drawings
Fig. 1 is the HBT-C before and after addition SDBS18Hypothesis Mathematical Model of heaped-up.With AIE The fluorescence probe HBT-C of matter18Detection anion surfactant is lighted by forming micella.
Fig. 2 (A) is HBT-C18In H2O/DMSO(99:1, v/v) the normalized ultraviolet suction in solution Receive spectrum；(B) it is HBT-C18In H2O/DMSO(99:1, v/v) the fluorescence hair in solution and under solid-state Penetrate spectrum.[HBT-C18]=5 μM；λex=334nm.
Fig. 3 (A) is with the increase HBT-C of SDBS concentration18(5 μM) are in H2O/DMSO(99:1, V/v the fluorescent emission spectrogram in solution)；(B) it is with the increase of SDBS concentration, HBT-C18510 Fluorescent emission intensity change at nm and 450nm；(C) it is with the increase of SDBS concentration, HBT-C18 Ratio (the I of fluorescent emission intensity at 510nm and 450nm510/I450) change.λex=334nm.
Fig. 4 is HBT-C18(5 μM) are in H2O/DMSO(99:1, v/v) with the glimmering of SDBS change in concentration in Quantum yield.
Fig. 5 is HBT-C18(A) normalization of (0,2.0,8.0 μM) is ultraviolet under different SDBS concentration inhales Receive and (B) fluorescence emission spectrogram of compound.[HBT-C18]=5 μM；λex=334nm.
Fig. 6 is HBT-C18Ratio (the I of fluorescent emission intensity at 510nm and 450nm510/I450) with The change of SDBS concentration.λexIt is equation of linear regression inside=334nm..
Fig. 7 (A) is HBT-C18(I at 510nm and 450nm510/I450) fluorescent emission intensity ratio Example is mapped to the logarithm of SDBS concentration；(B) it is the micella particle diameter measured by dynamic light scattering, PDI= 0.434；(C), (D) is HBT-C18(5 μM)/SDBS (8 μM) is in H2O/DMSO(99:1, v/v) it is molten (C) SEM and (D) TEM figure of the micella formed in liquid.
Fig. 8 is the HBT-C in the presence of different surfaces activating agent and ion18In 510nm and 450nm Ratio (the I of the fluorescent emission intensity at place510/I450) change.
Fig. 9 is light field and the stained photographs of the Escherichia coli under fluorescence.(HBT-C18=10 μM) engineer's scales= 10μm.
Figure 10 is E.coli bacteriums in various concentrations HBT-C18(0,10,20,40,60,80 and 100 μM) Under survival rate figure.
Embodiment
With reference to specific embodiment and Figure of description, the present invention is further elaborated.
Embodiment 1
According to following synthetic route, following compound is specifically synthesized：
(1) N- (3- formoxyl -4- hydroxybenzyls)-N, N- dimethyl stearyl -1- ammonium chlorides (compound 3) Synthesis
Under reflux conditions by 5- (chloromethyl) -2- hydroxyls salicylide (340mg, 2mmol) and N, N- dimethyl The mixture of octadecane -1- amine (594mg, 2mmol) is stirred 5 hours.After completion of the reaction, precipitation is filtered out And washed with ether (10mL × 2), it is dried under vacuum and obtains white solid product compound 3, yield is 90% (841mg).
1H NMR(CDCl3,500MHz):δ 11.26 (br s, 1H), 8.16 (d, J=3.5Hz, 1H), 7.80 (d, J=8.5Hz, 1H), 7.09 (d, J=8.5Hz, 1H), 5.21 (d, J=8.5Hz, 2H), 3.47 (t, J= 8.5Hz, 2H), 3.27 (s, 6H), 1.26-1.25 (m, 32H), 0.88 (t, J=7.0Hz, 3H)；13C NMR (d6-DMSO,125MHz):190.0,162.3,140.1,132.9,122.5,118.8,118.0,65.3,63.1, 48.7,31.3,29.0,29.0,28.9,28.76,28.66,28.5,25.8,22.1,21.7,13.9；HRMS(ESI): m/z[M-Cl]+Calculated value is C28H50NO2:432.3836；Actual measured value is:432.3845.
(2) N- (3- (benzo [d] thiazol-2-yl) -4- hydroxybenzyls)-N, N- dimethyl stearyl -1- ammonium chlorides (HBT-C18) synthesis
In N- (3- formoxyl -4- hydroxybenzyls)-N, N- dimethyl stearyl -1- ammonium chlorides (467mg, 1.0 Mmol) and in the methanol solution of 2- aminothiophenols (150mg, 1.2mmol) add dense HCl (37wt.%, 100mg, 1.0mmol), gained mixed liquor is stirred at room temperature 10 minutes.Then added in mixed liquor H2O2(30wt.%, 113mg, 1.0mmol), and be further stirred at room temperature 2 hours.Reacting Cheng Hou, evaporates solvent, and gained residue is recrystallized with dichloromethane/n-hexane, obtains white solid product N- (3- (benzo [d] thiazol-2-yl) -4- hydroxybenzyls)-N, N- dimethyl stearyl -1- ammonium chlorides (HBT-C18) (120mg, yield 21%)
1H NMR(CDCl3,500MHz):δ 12.87 (br s, 1H), 8.28 (s, 1H), 7.97 (d, J=8.0 Hz, 1H), 7.85 (d, J=7.5Hz, 1H), 7.63 (d, J=8.0Hz, 1H), 7.49 (t, J=8.0Hz, 1H), 7.40 (t, J=8.0Hz, 1H), 7.15 (d, J=7.0Hz, 1H), 5.17 (s, 2H), 3.47 (t, J=7.5Hz, 2H), 3.31 (s, 6H), 1.26-1.23 (m, 32H), 0.88 (t, J=7.0Hz, 3H)；
13C NMR(CDCl3,125MHz):168.2,159.7,136.8,133.7,132.7,126.9,126.0, 122.1,121.8,118.8,118.2,117.3,67.0,63.8,49.6,31.9,29.69,29.65,29.6,29.4, 29.4,29.3,26.4,22.9,22.7,14.1；HRMS(ESI):m/z[M-Cl]+Calculated value is C34H53N2OS:537.3873；Actual measured value is:537.3880.
Fig. 2 (A) is HBT-C18In H2O/DMSO(99:1, v/v) the normalized UV absorption in solution Spectrum；Fig. 2 (B) is HBT-C18In H2O/DMSO(99:1, v/v) fluorescence in solution and under solid-state Emission spectrum.[HBT-C18]=5 μM；λex=334nm. as can be seen from Figure, in solution state, is only seen The alcohol of formula at about 450nm is observed to light.This is due to that environmental disturbances in aqueous are caused.Solid-state During powder, lighting by force with big Stokes displacements (176nm) is observed in 510nm, comes from and excites State intermolecular proton transfer (ESIPT) process, and due to intramolecular hydrogen bond protected and its free movement by To suppression, therefore it can launch strong keto-acid and light.Big Stokes displacements (176nm) are excitation state The characteristic feature of intermolecular proton transfer (ESIPT) process.HBT-C18In H2O/DMSO (volume ratios 99:1) quantum yield in solution and under solid-state is respectively 0.2% and 50.5%, has clearly demonstrated that its AIE Property.
Embodiment 2：The detection of anion surfactant
HBT-C prepared by 15 μ L embodiments 118DMSO (1.0mM) mother liquor add 2.985mL In pure water containing different content anionic surfactant sodium dodecylbenzene sulfonate (SDBS), whirlpool shake 10s is swung, fluorescence (excitation wavelength 334nm) is determined with fluorescence spectrometer.
Fig. 3 (A) is with the increase HBT-C of SDBS concentration18(5 μM) are in H2O/DMSO(99:1, V/v the fluorescent emission spectrogram in solution)；(B) it is with the increase of SDBS concentration, HBT-C18 Fluorescent emission intensity change at 510nm and 450nm；(C) be with the increase of SDBS concentration, HBT-C18Ratio (the I of fluorescent emission intensity at 510nm and 450nm510/I450) change.λex=334 nm.
Fig. 4 is HBT-C18(5 μM) are in H2O/DMSO(99:1, v/v) with the glimmering of SDBS change in concentration in Quantum yield.As can be seen from Figure, HBT-C18Fluorescence quantum yield increase to 8.5% from 0.2%. This is due to form zwitterion aggregation, and intramolecular hydrogen bond is protected.
Fig. 5 is HBT-C18(A) normalization UV absorption of (0,2.0,8.0 μM) under different SDBS concentration (B) fluorescence emission spectrogram of compound.[HBT-C18]=5 μM；λex=334nm. as can be seen from Figure, is adding Enter after SDBS, disappeared in the absorption spectrum of 370nm~420nm tailing peak, intramolecular hydrogen bond is protected, Send strong keto-acid fluorescence.
Fig. 6 is HBT-C18Ratio (the I of fluorescent emission intensity at 510nm and 450nm510/I450) with The change of SDBS concentration.The luminous ratio detected as can be seen from Figure in 450nm and 510nm (I510/I450) gradually increase compared with the increased amounts of SDBS.λexIt is equation of linear regression inside=334nm.. Computational methods based on signal to noise ratio, the test limit (3 δ/S) for SDBS is 0.05 μM, far below based on Asia The national standard of methyl blue AAS (test limit is about 0.14 μM).
Fig. 7 (A) is HBT-C18(I at 510nm and 450nm510/I450) fluorescent emission intensity ratio Example is mapped to the logarithm of SDBS concentration；As illustrated, in HBT-C18Negative and positive in/SDBS mixed systems The critical concentration of ionic micelle is 2.39 μM, substantially less than SDBS critical micelle concentration (1.2mM).
Fig. 7 (B) is the micella particle diameter measured by dynamic light scattering (DLS), PDI=0.434.Shown in figure, The diameter average out to 223.8nm of micella.
Fig. 7 (C), (D) are HBT-C18(5 μM)/SDBS (8 μM) is in H2O/DMSO(99:1, v/v) it is molten The ESEM (SEM) and transmission electron microscope (TEM) figure of the micella formed in liquid.Show that micella is in figure Spherical structure, its radius is 90~200nm, and the result relative to DLS, the micelle diameters measured are smaller, This is due in Sample Preparation Procedure, to be changed into dry state by solution state, and solution evaporation can cause glue What the contraction of beam was caused.
Embodiment 3：
The detection of different surfaces activating agent and ion
HBT-C prepared by 15 μ L embodiments 118DMSO (1.0mM) mother liquor add 2.985mL Contain different surfaces activating agent and ion (neopelex (SDBS), lauryl sodium sulfate (SDS), triton x-100, cetrimonium bromide (CTAB) and simple ion be (such as：Na+, K+,Mg2+,Ca2+,Zn2+NO3 –,HCO3 –,HCO3 2–,PO4 3–,SO4 2–)) pure water in, whirlpool concussion 10s, fluorescence (excitation wavelength 334nm) is determined with fluorescence spectrometer.As a result it is as shown in Figure 8.
Fig. 8 is the HBT-C in the presence of different surfaces activating agent and ion18In 510nm and 450nm Ratio (the I of the fluorescent emission intensity at place510/I450) change.The probe is to being connected with sulfonic anion surface active Agent has very high sensitivity, including：Neopelex (SDBS), lauryl sodium sulfate (SDS), And the surfactant triton x-100 and cationic surfactant cetrimonium bromide of centering (CTAB), and a variety of simple cations (such as：Na+,K+,Mg2+,Ca2+,Zn2+), anion (such as：NO3 –,HCO3 –,HCO3 2–,PO4 3–,SO4 2–) then respond it is very weak.
Embodiment 4：Bacterial fluorescence is dyed
(1) Bacteria Culture
Escherichia coli (E.coli, strain ATCC 15224) are bought from VWR International, LLC.Will The single bacterium colony of the bacterium is seeded in 5mL LB matrix, and (150rpm) is shaken at 37 DEG C.Afterwards, 1mL bacterial suspensions are inoculated into 50mL fresh matrix, 5h is cultivated under being shaken at 37 DEG C, with Realize that mid-log phase grows.
(2) E.coli fluorescent staining
E.coli is cultivated 12 hours at 37 DEG C, by PBS by the concentration dilution of bacterium to 107 CFU/mL, the HBT-C then prepared with 10 μM of embodiments 118Cultivated 0.5 hour at 37 DEG C.With Confocal Laser Scanning Microscopy carries out fluorescence imaging experiments (Leica TCS-SP8, Germany), 405 Nm is excited and is used 508-558nm optical filter.As a result it is as shown in Figure 9.
Fig. 9 is light field and the stained photographs of the Escherichia coli under fluorescence.(HBT-C18=10 μM) engineer's scales= 10 μm of as can be seen from Figure, under laser scanning co-focusing microscope, the fluorogram of shown Escherichia coli As high-visible, the influence of background noise can be ignored.Therefore HBT-C18Probe can be used for direct staining Bacterium is without further separation, washing step.
(3) antibacterial experiment
HBT-C prepared by the embodiment 1 of various concentrations18It is 10 that probe, which adds 1mL bacterial concentrations,7 In CFU/mL LB media, HBT-C is determined18Antibacterial activity.(150rpm) is shaken at 37 DEG C 2h is cultivated, resulting solution is diluted with 9mL PBS.After roughly being mixed with pipettor, solution is transferred to In 15mL test tube, further eddy oscillating mixed cell 3min.Then, the bacterial solution is diluted 100,101With 102Times, the bacterial suspension for then taking 10 μ L to dilute assesses the work of bacterium with agar plate Property.
Figure 10 is E.coli bacteriums in various concentrations HBT-C18(0,10,20,40,60,80 and 100 μM) Under survival rate figure.It can be seen that HBT-C18Probe shows the poison of low-down directed toward bacteria Property, be conducive to the fluorescent staining of its directed toward bacteria to test.
Although with reference to preferred embodiment, the present invention is described, and the invention is not limited in above-mentioned implementation Example, it should be appreciated that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention.In addition It should be understood that after the content of the invention lectured has been read, those skilled in the art can be to present invention work Various changes or modification without departing substantially from present inventive concept, these equivalent form of values equally fall within right appended by the application Claim limited range.

Claims (10)

1. the compound shown in Formulas I：
Wherein：
R1, R2It is independently hydrogen, C1-18Alkyl, halogen, C1-18Alkyl oxy, C1-18Alkyl sulfenyl, virtue Base, heteroaryl；R3, R4, R5For C1-30Alkyl；R6For straight key, C1-6Alkylidene；A-For anion, For example：Halogen ion, perchlorate, sulfate ion, nitrate ion, hexafluorophosphoricacid acid ions etc..
2. compound according to claim 1, wherein, R1, R2It is independently hydrogen, C1-6Alkyl, Halogen, C1-6Alkyl oxy, C1-6Alkyl sulfenyl.
3. compound according to claim 1, wherein, R3, R4, R5In at least one be C8-30 Alkyl, more preferably C10-24Alkyl, and preferably C12-22Alkyl, or C14-20Alkyl.
It is preferred that, R3, R4, R5In a group be C8-30Alkyl, more preferably C10-24Alkyl, again Preferably C12-22Alkyl, or C14-20Alkyl；And another two group is C1-8Alkyl, more preferably C1-6Alkane Base.
4. compound according to claim 1, wherein, the formula I is below formula (Ia)：
Wherein, R1、R2、R3、R4、R5、A-It is as defined above.
It is preferred that, in Formulas I a, R1For hydrogen, R2For hydrogen, R3, R4For methyl, R5For octadecyl, A- For anion；
It is further preferred that compound of formula I is selected from：
N- (3- (benzo [d] thiazol-2-yl) -4- hydroxybenzyls)-N, N- dimethyl stearyl -1- ammonium chlorides.
5. a kind of preparation method of the compound described in any one of claim 1-4, including by Formula II compound With formula III compound under Protic Acid Catalyzed and oxidising agent oxidation, reaction obtains compound of formula I：
Wherein, R1、R2、R3、R4、R5、R6、A-As any one of claim 1-4 is defined.
It is preferred that, the Bronsted acid is concentrated hydrochloric acid, and the oxidising agent is hydrogen peroxide.
Preferably, the Formula II compound can be obtained by following preparation method, including：By formula IV chemical combination Thing obtains Formula II compound with the reaction of Formula V compound.
Wherein, R2、R3、R4、R5、R6、A-As any one of claim 1-4 is defined.
6. purposes of the compound in detection anion surfactant described in claim any one of 1-4.
7. purposes according to claim 6, wherein, described anion surfactant can be carboxylic acid Salt, sulfuric acid, sulfonate and phosphate ester salt, it is preferred that described anion surfactant is connection There are the anion surfactant of sulfonic acid group, such as neopelex (SDBS), dodecyl Sodium sulphate (SDS) etc..
8. a kind of method for detecting anion surfactant, including, in the solution of anion surfactant The middle compound added described in claim any one of 1-4, in observed under fluorescent light or detection fluorescence spectrum.
9. purposes of the compound in the disposable fluorescent staining of bacterium described in claim any one of 1-4；
It is preferred that, described bacterium is the bacterium surrounded with negative electrical charge outer membrane, such as Escherichia coli, withered grass Bacillus, staphylococcus aureus etc..
10. a kind of method of the disposable fluorescent staining of bacterium, including, by the change described in claim any one of 1-4 Compound is co-cultured with bacterium, and the fluorescent staining of bacterium can be directly observed without separation, for example, laser can be used to sweep Confocal microscope is retouched to be observed.
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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN110132915A (en) * 2019-05-10 2019-08-16 华南理工大学 A kind of method of aggregation-induced emission probe and double check heavy metal ion pollutant
CN110590701A (en) * 2019-10-08 2019-12-20 衡阳师范学院 Benzothiazole-phenethyl cyanide compound and preparation method and application thereof
CN111423851A (en) * 2020-02-17 2020-07-17 北京华泰诺安技术有限公司 Biological aerosol simulating agent and preparation method thereof
CN112480025A (en) * 2020-12-11 2021-03-12 汉中职业技术学院 Compound with aggregation-induced emission function and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Title
MINMIN CAI,ET AL: "A small change in molecular structure, a big difference in the AIEE mechanism", 《PHYS. CHEM. CHEM. PHYS.》 *
WEN LI,ET AL: "Tunable RGB luminescence of a single molecule with high quantum yields through a rational design", 《J. MATER. CHEM.》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110132915A (en) * 2019-05-10 2019-08-16 华南理工大学 A kind of method of aggregation-induced emission probe and double check heavy metal ion pollutant
CN110590701A (en) * 2019-10-08 2019-12-20 衡阳师范学院 Benzothiazole-phenethyl cyanide compound and preparation method and application thereof
CN110590701B (en) * 2019-10-08 2023-03-28 衡阳师范学院 Benzothiazole-phenethyl cyanide compound and preparation method and application thereof
CN111423851A (en) * 2020-02-17 2020-07-17 北京华泰诺安技术有限公司 Biological aerosol simulating agent and preparation method thereof
CN111423851B (en) * 2020-02-17 2023-09-08 北京华泰诺安技术有限公司 Biological aerosol simulator and preparation method thereof
CN112480025A (en) * 2020-12-11 2021-03-12 汉中职业技术学院 Compound with aggregation-induced emission function and preparation method and application thereof
CN112480025B (en) * 2020-12-11 2022-07-12 汉中职业技术学院 Compound with aggregation-induced emission function and preparation method and application thereof

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