CN105647523A - GSH (glutathione) sensor based on Rhodamine B and preparation and application thereof - Google Patents

GSH (glutathione) sensor based on Rhodamine B and preparation and application thereof Download PDF

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CN105647523A
CN105647523A CN201610197127.6A CN201610197127A CN105647523A CN 105647523 A CN105647523 A CN 105647523A CN 201610197127 A CN201610197127 A CN 201610197127A CN 105647523 A CN105647523 A CN 105647523A
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compound
optical sensor
gsh
fluorescent optical
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CN105647523B (en
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包晓峰
吴小磊
舒海
曹乾升
史加新
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Nanjing University of Science and Technology
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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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
    • G01N21/6408—Fluorescence; Phosphorescence with measurement of decay time, time resolved fluorescence
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
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    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen

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Abstract

The invention discloses a GSH (glutathione) fluorescent sensor based on Rhodamine B and preparation and application thereof. Rhodamine B is used as a precursor to synthesize a target product: N-(2-(3'-6'-bis(diethylamino)-3-oxo-spiro[isoindoline-1,9'-xanthene]-2-ethyl)-3,5-bis(2,5-dioxo-3,4-pyrroline)benzamide. The invention provides application of the target product in detecting glutathione, it is discovered that the target product can well detect the glutathione, materials used herein are easy to obtain, synthetic steps are simple, post-treatment is also convenient, and large-scale production is easy to implement.

Description

A kind of based on the GSH sensor of rhodamine B, preparation and application
Technical field
The invention belongs to biochemical field, be specifically related to a kind of based on the GSH fluorescent optical sensor of rhodamine B, preparation and application.
Background technology
Glutathion (GSH) is extensively in that in animal and plant have important effect in vivo. GSH chemical, biological defense system in human body plays an important role, and has many-sided physiological function. Its major physiological effect is able to the free radical disposing in human body, as internal a kind of important antioxidant, the sulfydryl in protection numerous protein and enzyme equimolecular. In addition GSH also has the functions such as removing toxic substances, the liver protecting, radioprotective, enhancing immunity, antiallergic. Lack GSH in human body and can cause many health problems, for instance: skin injury, trichochromes depigmentation, hepatic injury etc. In view of GSH is so most important to human body, study a kind of method tool that quick and convenient can detect GSH and be of great significance.
At present, the method of detection GSH mainly has: spectrophotography, fluorescence method, high performance liquid chromatography (HPLC) method, high performance capillary electrophoresis (HPCE), Flow cytometry etc., but there is a lot of shortcoming in these methods, as required instrument price costly takes, inconvenient to carry, sensitivity is poor, and the GSH concentration range measured is little, for measuring then difficulty etc. especially in the cell that the amount containing GSH is less. In contrast, owing to chemiluminescence does not need any light source, thus when fluorescent probe being carried out chemiluminescence imaging detection, it is absent from the interference of inevitable optics background when fluoroscopic examination or fluorescence imaging, it is hereby achieved that less detection limit.
Dye stuff of rhodamine kinds is bigger due to its molar absorption coefficient, fluorescence quantum yield is high, spectrum property is superior, simple in construction, be prone to advantages such as modifying, absorbing wavelength scope is wide, being widely used and molecular probe designs, at present, rhodamine molecular probe is used for detection Al3+, Cr3+, GSH etc.
Document 1(LiuX, ZhangW, LiC, etal.NanomolardetectionofHcy, GSHandCysinaqueoussolution, testpaperandlivingcells [J] .RscAdvances, 2014,7:4941-4946.) reporting one utilizes naphthalimide analog derivative and sulfonic acid chloride to carry out condensation, a kind of method synthesizing novel GSH sensor, productivity 54.8%.
Document 2(KimGJ, LeeK, KwonH, etal.RatiometricFluorescenceImagingofCellularGlutathione [J] .OrganicLetters, 2011,13 (11): 2799-2801.) reporting one utilizes coumarin derivative and phenol derivatives to carry out condensation, a kind of method synthesizing novel GSH sensor, productivity 60%.
(1) in document 1, selectivity is not especially good, Hcy, Cyst also has response, and effect and GSH are suitable, and productivity is not high.
(2) in document 2, buffer concentration is too low, only 0.1mM. Very difficult guarantor tests in neutral conditions.
Drawbacks described above causes up to now, and applying existing process, to be difficult to obtain synthesis simple, and productivity is high and the good GSH transducer production method of selectivity.
Summary of the invention
It is an object of the invention to provide a kind of based on the GSH fluorescent optical sensor of rhodamine B, preparation and application.
The technical solution realizing the object of the invention is:
A kind of GSH fluorescent optical sensor based on rhodamine B, the structure of this fluorescent optical sensor is as follows:
��
The preparation method of the GSH fluorescent optical sensor based on rhodamine B of said structure, comprise the following steps: under room temperature, compound 2, compound 4, catalyst of triethylamine are reacted in organic solvent, after having reacted, removal of solvent under reduced pressure, extract, silicagel column separates, obtaining pale yellow powder and be target compound GSH fluorescent optical sensor, wherein, the structure of compound 2 and compound 4 is as follows:
��
In the present invention, compound 2, compound 5, catalyst of triethylamine mol ratio be 1.2:1:2
In the present invention, response time 2-3h.
In the present invention, organic solvent is selected from ethanol, methanol, acetonitrile, any one in dichloromethane.
In the present invention, the eluent in silicagel column separation adopts MeOH:CH2Cl2The mixed liquor of=1:99.
In the present invention, the described GSH fluorescent optical sensor based on rhodamine B is for detecting the glutathion of organism.
Compared with prior art, it has the remarkable advantages that the present invention: (1) present invention has synthesized a kind of novel GSH fluorescent optical sensor with rhodamine for main body, has good light stability, long wavelength emission and quantum yield advantages of higher. (2) cost of material selected by the present invention is low, and synthesis step is simple, and post processing is also very convenient, is easier to realize large-scale production. (3) present invention adopts acyl chlorides and primary amine condensation reaction mode, and synthetic method is simple, and reaction condition is gentle, and productivity is higher. (4) the sensor property of can select that involved in the present invention detection GSH, and sensitivity is higher, has great application prospect in detecting intracellular GSH.
Accompanying drawing explanation
Fig. 1 is the compound 2 of the present invention1HNMR��
Fig. 2 is the compound 2 of the present invention13CNMR��
Fig. 3 is the compound 3 of the present invention1HNMR��
Fig. 4 is the compound 3 of the present invention13CNMR��
Fig. 5 is the compound 5 of the present invention1HNMR��
Fig. 6 is the compound 5 of the present invention13CNMR��
Fig. 7 is the fluorescence selectivity test figure of the compound 5 of the present invention.
Fig. 8 is the time stability test figure of the compound 5 of the present invention.
Detailed description of the invention
(1) synthesis of sensor compound
The invention provides target product application in GSH detects, it has been found that GSH is had good Detection results by it. Synthetic route of the present invention is as follows:
��
(2) fluorescence property test
By GSH, Cys, Hcy, Lys, Ser, Gln, the different aminoacids such as Gly adds in the solution of compound 5, carries out fluorescence response test.
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
The preparation method of a kind of GSH fluorescent optical sensor based on rhodamine B of the present invention, comprises the following steps:
The first step, reflux more than 12h by rhodamine B and excessive ethylenediamine in dehydrated alcohol, after having reacted, removal of solvent under reduced pressure, extract, silicagel column separates, and finally obtains pale yellow powder namely compound 2,
The structure of compound 2 is as follows:
;
Second step, reflux 20h by 3,5-diaminobenzoic acids and maleic anhydride in chloroform, after having reacted, it is filtered to remove solvent, dries filter cake, obtaining yellow greenish powder, then react 2h in acetic anhydride with anhydrous sodium acetate, temperature is 100 DEG C, after having reacted, reactant liquor is poured in frozen water, continue stirring 1h, then it is filtered to remove solvent, and by water flush cake 10 times, finally obtains pale asphyxia pressed powder, namely compound 3
The structure of compound 3 is as follows:
;
3rd step, refluxes the compound 3 obtained in second step overnight in thionyl chloride, after having reacted, and removal of solvent under reduced pressure, obtain white powder namely compound 4,
The structure of compound 4 is as follows:
;
4th step, under room temperature, the compound 2 that will obtain in the first step, the compound 5 obtained in the 4th step, triethylamine reacts in dichloromethane, after having reacted, and removal of solvent under reduced pressure, extracting, silicagel column separates, and obtains pale yellow powder and is described GSH fluorescent optical sensor.
The synthesis of embodiment 1 fluorescence chemical sensor
1. the synthesis of compound 2
By rhodamine B (960mg, 2mmol) with ethylenediamine (1.3ml, 20mmol) in dehydrated alcohol (40ml), controlling reaction temperature at 80 DEG C, the response time is 12h, after having reacted, removal of solvent under reduced pressure, extract, separate through silicagel column and obtain faint yellow solid (880mg, 92%). Compound 21HNMR,13CNMR is respectively as shown in Fig. 1, Fig. 2.
2. the synthesis of compound 3
By 3,5-diaminobenzoic acids (200mg, 1.31mmol) and maleic anhydride (385mg, 3.93mmol) back flow reaction 20h in chloroform. Reaction is filtered to remove solvent after terminating, and solid obtains greenish yellow solid, reacts 2h, temperature 100 DEG C with anhydrous sodium acetate (35.1mg, 0.43mmol) in acetic anhydride after drying. After reaction, mixed liquor is joined in frozen water, continue stirring 1h. Afterwards, sucking filtration removes liquid, by water flush cake repeatedly, dries, obtains pale asphyxia solid (170mg, 42%). Compound 31HNMR,13CNMR is Fig. 3 such as, shown in Fig. 4.
3. the synthesis of compound 5
By compound 3(50mg, 0.16mmol) back flow reaction 12h in thionyl chloride, removal of solvent under reduced pressure, obtain white solid 4(49mg, 93%).
4. the synthesis of compound 6
By compound 4(45mg, 0.14mmol) and compound 2(87.60mg, 0.18mmol) react in dichloromethane, add 48ul triethylamine (0.27mmol), room temperature reaction 2.5h. After having reacted, removal of solvent under reduced pressure, extract, separate through silicagel column and obtain faint yellow solid (55mg, 52%). Compound 51HNMR,13CNMR is respectively as shown in Fig. 5, Fig. 6.
Embodiment 2 fluorescence selectivity can be tested
GSH fluorescent optical sensor 5 has good dissolubility, empirical tests in ethanol, and compound 5 is soluble in EtOH:HEPES(0.6mM, pH=7.2) in=3:2 mixed liquor, preparation this solution of 500ml is as storing solution (pH=7.2).
Accurately configuration GSH fluorescent optical sensor 5 is 1 �� 10-3mol/LEtOH-H2O mixed liquor (3/2, V/V), Amino Acid GS H, Cys, Hcy, Lys, Ser, Gln, Gly isoconcentration is 5 �� 10-3Mol/L aqueous solution, and with EtOH:HEPES(0.6mM, pH=7.2,3/2, V/V) solution.
Fluorescence selectivity is tested as shown in Figure 6, take 3ml storing solution and be placed in liquid cell, add 120uLGSH to fluorescent optical sensor 5 solution, survey its initial fluorescent intensity value, be then respectively adding the various Freamine �� 120uL configured, measure its stable time fluorescence intensity.Observe Fig. 7 it can be seen that GSH is obvious responsed to effect by compound 5, and reach maximum in 588nm place fluorescence intensity, namely GSH is had good selectivity by compound 5.
Embodiment 3 time stability
Fluorescent optical sensor 5 has good dissolubility, empirical tests in ethanol, and compound 5 is soluble in MeOH:HEPES(0.6mM, pH=7.2) in=3:2 mixed liquor, preparation this solution of 500ml is as storing solution (pH=7.2).
Accurately configuration GSH fluorescent optical sensor 5 is 1 �� 10-3mol/LEtOH-H2O mixed liquor (3/2, V/V), Amino Acid GS H concentration is 5 �� 10-3Mol/L aqueous solution, and with EtOH:HEPES(0.6mM, pH=7.2,3/2, V/V) solution.
Time stability is tested as it can be seen, take 3ml storing solution and be placed in liquid cell, adds 120uLGSH to fluorescent optical sensor 5 solution, surveys its initial fluorescent intensity value, then measure its fluorescence intensity every a few minutes, until stable. Observe Fig. 8 it can be seen that GSH is reached stable being approximately in 50min by compound 5.

Claims (7)

1. a fluorescent optical sensor, it is characterised in that the chemical constitution of this fluorescent optical sensor is as follows:
��
2. the preparation method of a fluorescent optical sensor as claimed in claim 1, it is characterized in that, comprise the following steps: under room temperature, compound 2, compound 4, catalyst of triethylamine are reacted in organic solvent, after having reacted, removal of solvent under reduced pressure, extracting, silicagel column separates, and obtains sensor of interest, wherein, the structure of compound 2 and compound 4 is as follows:
��
3. the preparation method of fluorescent optical sensor as claimed in claim 2, it is characterised in that the mol ratio of compound 2, compound 5 and catalyst of triethylamine is 1.2:1:2.
4. the preparation method of fluorescent optical sensor as claimed in claim 2, it is characterised in that the response time is 2-3h.
5. the preparation method of fluorescent optical sensor as claimed in claim 2, it is characterised in that organic solvent is selected from ethanol, methanol, acetonitrile, any one in dichloromethane.
6. the preparation method of fluorescent optical sensor as claimed in claim 2, it is characterised in that the eluent in silicagel column separation adopts MeOH:CH2Cl2The mixed liquor of=1:99.
7. claim 1-6 arbitrarily as described in fluorescent optical sensor detection organism glutathion in application.
CN201610197127.6A 2016-03-31 2016-03-31 A kind of GSH sensors, preparation and application based on rhodamine B Expired - Fee Related CN105647523B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106146526A (en) * 2016-07-14 2016-11-23 南京工业大学 Fluorescent probe compound and preparation method and application thereof
CN106243118A (en) * 2016-06-17 2016-12-21 南京理工大学 A kind of GSH sensor based on rhodamine B, preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004025268A2 (en) * 2002-09-13 2004-03-25 Carnegie Mellon University Optical biosensors and methods of use thereof
CN103951673A (en) * 2014-05-08 2014-07-30 山西大学 Reagent and application thereof in mercaptan detection

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004025268A2 (en) * 2002-09-13 2004-03-25 Carnegie Mellon University Optical biosensors and methods of use thereof
CN103951673A (en) * 2014-05-08 2014-07-30 山西大学 Reagent and application thereof in mercaptan detection

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HAILANG CHEN等: "Synthesis of a new highly sensitive near-infrared fluorescent iridium(III) probe and its application for the highly selective detection of glutathione", 《RSC ADV.》 *
VLADIMIR N.BELOV等: "Rhodamine Spiroamides for Multicolor Single-Molecule Swithching Fluorescent Nanoscopy", 《CHEM.EUR.J.》 *
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106243118A (en) * 2016-06-17 2016-12-21 南京理工大学 A kind of GSH sensor based on rhodamine B, preparation method and application
CN106146526A (en) * 2016-07-14 2016-11-23 南京工业大学 Fluorescent probe compound and preparation method and application thereof
CN106146526B (en) * 2016-07-14 2018-09-21 南京工业大学 Fluorescent probe compound and preparation method and application thereof

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