CN107011351A - Fe3+Fluorescent optical sensor, preparation method and applications - Google Patents

Fe3+Fluorescent optical sensor, preparation method and applications Download PDF

Info

Publication number
CN107011351A
CN107011351A CN201710333730.7A CN201710333730A CN107011351A CN 107011351 A CN107011351 A CN 107011351A CN 201710333730 A CN201710333730 A CN 201710333730A CN 107011351 A CN107011351 A CN 107011351A
Authority
CN
China
Prior art keywords
optical sensor
fluorescent optical
rhodamine
preparation
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201710333730.7A
Other languages
Chinese (zh)
Inventor
包晓峰
华青涵
周彤
陈相雪
王宇
吴小磊
舒海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University of Science and Technology
Original Assignee
Nanjing University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing University of Science and Technology filed Critical Nanjing University of Science and Technology
Priority to CN201710333730.7A priority Critical patent/CN107011351A/en
Publication of CN107011351A publication Critical patent/CN107011351A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The invention discloses a kind of Fe3+Fluorescent optical sensor, preparation method and application.The present invention is with rhodamine B（Rhodanmine B) for the precursor synthesis target product N (thioamides of 2 (3 ', 6 ' double (diethylamino) oxaspiros [second of the xanthene of iso-indoles 1,9 ' 2) 1 hydrogen imidazoles 1.The invention provides target product in Fe3+Application in detection, finds it to Fe3+There are good Detection results, compared with prior art, the raw material that the present invention is used is easy to get, and synthesis step is simple, and post processing is also very convenient, be easier to realize large-scale production, in detection Fe3+Aspect has very big application prospect.

Description

Fe3+Fluorescent optical sensor, preparation method and applications
Technical field
The invention belongs to biochemical field, and in particular to a kind of Fe3+Fluorescent optical sensor, preparation method and application.
Background technology
At present, Fe is detected3+Method mainly have：Atomic absorption spectrophotometry, voltammetry, colorimetric method and flow injection Method, but there are many shortcomings in these methods, such as required instrument price is costly time-consuming, and inconvenient to carry, sensitiveness is poor, is surveyed Fixed Fe3+Concentration range is little, for containing Fe3+Measure and even more difficulty etc. is measured then in less cell.In contrast, due to changing Learn it is luminous does not need any light source, thus when carrying out chemiluminescence imaging detection to fluorescence probe, in the absence of fluoroscopic examination or The interference of inevitable optics background during person's fluorescence imaging, it is hereby achieved that lower detection limit.
Dye stuff of rhodamine kinds is larger due to its molar absorption coefficient, and fluorescence quantum yield is high, spectrum property is superior, structure is simple It is single, be easy to the advantages such as modification, absorbing wavelength scope be wide, be widely used and molecular probe designed, at present, rhodamine point Sub- probe is used for detecting Al3+, Cr3+, Zn2+Deng.
(Weerasinghe A J, Schmiesing C, Varaganti S, the et al.Single-and of document 1 multiphoton turn-on fluorescent Fe(3+)sensors based on bis(rhodamine).[J] .J.phys.chem.b,2010,114(29):A kind of rhodamine hydrazides and aldehyde radical thing condensation reaction 9413-9419..) are reported, Synthesize a kind of new Fe3+The method of sensor, yield 85%.
(Yang M, Meng W, Ding Q, the et al.Novel fluorescent probes based on of document 2 rhodamine for naked-eye detection of Fe3+and their application of imaging in Living cells [J] .New Journal of Chemistry, 2015,39.) report and a kind of utilize rhodamine B and amino Condensation reaction synthesizes a kind of new Fe3+The method of sensor, yield 49%.
There is following defect in the synthetic method that above-mentioned document is reported
(1) as in document 1, the probe water solubility of synthesis is poor, and 75% is all acetonitrile.
(2) as in document 2, the yield of the probe of synthesis is relatively low, and only 49%.
Drawbacks described above causes up to now, to be difficult to obtain that production cost is low, fluorescence intensity is high, choosing using existing process method The preferable Fe of selecting property3+Transducer production method.
The content of the invention
It is an object of the present invention to provide a kind of Fe3+Fluorescent optical sensor, preparation method and application.
Realizing the technical solution of the object of the invention is：
A kind of Fe3+Fluorescent optical sensor, the structure of the fluorescent optical sensor is as follows：
Fe based on rhodamine B in the present invention3+The preparation method of fluorescent optical sensor, comprises the following steps：
By rhodamine ethylenediamine and 1,1 '-thio-carbonyldiimidazole is dissolved in dichloromethane, normal-temperature reaction 30- at normal temperatures 40min, after reaction is completed, removal of solvent under reduced pressure, extraction, silica gel post separation, it is the Fe to obtain white powder3+Fluorescence is passed Sensor.
In the present invention, rhodamine ethylenediamine and 1, the mol ratio of 1 '-thio-carbonyldiimidazole is 1：1.
In the present invention, the eluent that silica gel post separation is used is MeOH：CH2Cl2=1：99(v/v).
The heretofore described Fe based on rhodamine B3+Fluorescent optical sensor is used to detect Fe3+。
Compared with prior art, its remarkable advantage is the present invention：(1) present invention has synthesized a kind of new by main body of rhodamine Type Fe3+Fluorescent optical sensor, with good photostability, the advantages of long wavelength emission and high quantum yield.(2) institute of the present invention Low from cost of material, synthesis step is simple, and post processing is also very convenient, is easier to realize large-scale production.(3) present invention uses halogen For hydrocarbon and primary amine condensation reaction mode, synthetic method is simple, and reaction condition is gentle, and yield is higher.(4) it is involved in the present invention to pass Sensor energy selective enumeration method Fe3+Change, and sensitivity is higher, the Fe in detection environment3+Aspect has before very big application Scape.
Brief description of the drawings
Fig. 1 is the 1H NMR of compound 2 of the invention.
Fig. 2 is the 13C NMR of compound 2 of the invention.
Fig. 3 is the fluorescence selectivity of the compound 2 of the present invention.
Fig. 4 is the ultraviolet selectivity of the compound 2 of the present invention.
Embodiment
(1) synthesis of sensor compound
The invention provides target product in Fe3+Application in detection, finds it to Fe3+There are good Detection results.This Invention synthetic route is as follows：
(2) fluorescence property is tested
By CdCl2·2.5H2O,CuCl2·2H2O,AlCl3,KCl,FeCl3·6H2O,PbCl2,AgNO3,HgCl2, NiCl2·6H2O,MgCl2·6H2O,NaCl,ZnCl2,CrCl3·6H2O,Ba(NO3)2,MnCl2·4H2O,CaCl2, CoCl2· 6H2O,CaCl2In the solution that compound 2 is added etc. different heavy metal ion, fluorescence response test is carried out.
(3) ultraviolet test
By CdCl2·2.5H2O,CuCl2·2H2O,AlCl3,KCl,FeCl3·6H2O,PbCl2,AgNO3,HgCl2, NiCl2·6H2O,MgCl2·6H2O,NaCl,ZnCl2,CrCl3·6H2O,Ba(NO3)2,MnCl2·4H2O,CoCl2·6H2O, CaCl2In the solution that compound 3 is added etc. different heavy metal ion, ultraviolet response test is carried out
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The synthesis of fluorescence chemical sensor
1. the synthesis of compound 1
By rhodamine B (960mg, 2mmol) and ethylenediamine (1.3ml, 20mmol) in absolute ethyl alcohol (40ml), control is anti- Answer temperature at 80 DEG C, the reaction time is 12-13h.After reaction is completed, removal of solvent under reduced pressure, extraction is isolated through silicagel column Faint yellow solid (880mg, 92%).
2. the synthesis of compound 2
Compound 1 (135.6mg, 0.28mmol) and 1,1 '-thio-carbonyldiimidazole (50mg, 0.28mmol) are dissolved in two Chloromethanes (8ml), normal-temperature reaction 30-40min.After reaction is completed, removal of solvent under reduced pressure, extraction is isolated through silicagel column Purple powder (133mg, 80%).Compound 21H NMR,13C NMR are respectively such as Fig. 1, shown in Fig. 2.
Embodiment 2
Fluorescence selectivity can be tested
Fe3+Fluorescent optical sensor 2 has good dissolubility in ethanol, and empirical tests, compound 2 is soluble in EtOH： HEPES (1mM, pH=7.2)=2：In 1 mixed liquor, prepare the 500ml solution and be used as storing solution (pH=7.2).
Accurate configuration Fe3+Fluorescent optical sensor 2 is 1 × 10-3mol/L EtOH-H2O mixed liquors (2/1, V/V), CdCl2· 2.5H2O,CuCl2·2H2O,AlCl3,KCl,FeCl3·6H2O,PbCl2,AgNO3,HgCl2,NiCl2·6H2O,MgCl2· 6H2O,NaCl,ZnCl2,CrCl3·6H2O,Ba(NO3)2,MnCl2·4H2O,CoCl2·6H2O,CaCl2Isoconcentration is 5 × 10- 3The mol/L aqueous solution, and use EtOH：HEPES (1mM, pH=7.2,2/1, V/V) solution.
Fluorescence selectivity is tested as shown in figure 3, take 3ml storing solutions to be placed in liquid cell, adds 60uL fluorescent optical sensors 2, Survey its initial fluorescent intensity value, be then respectively adding the various positive 60uL configured, measure its it is stable when fluorescence intensity.Observation Fig. 3 understands that compound 2 is to Fe3+Effect is obvious responsed to, and fluorescence intensity reaches maximum, namely compound at 582nm 2 couples of Fe3+There is good selectivity.
Embodiment 3
Ultraviolet selection performance test
Fe3+Fluorescent optical sensor 2 has good dissolubility in ethanol, and empirical tests, compound 2 is soluble in EtOH： HEPES (1mM, pH=7.2)=2：In 1 mixed liquor, prepare the 500ml solution and be used as storing solution (pH=7.2).
Accurate configuration Fe3+Fluorescent optical sensor 2 is 1 × 10-3mol/L EtOH-H2O mixed liquors (2/1, V/V), CdCl2· 2.5H2O,CuCl2·2H2O,AlCl3,KCl,FeCl3·6H2O,PbCl2,AgNO3,HgCl2,NiCl2·6H2O,MgCl2· 6H2O,NaCl,ZnCl2,CrCl3·6H2O,Ba(NO3)2,MnCl2·4H2O,CoCl2·6H2O,CaCl2Isoconcentration is 5 × 10- 3The mol/L aqueous solution, and use EtOH：HEPES (1mM, pH=7.2,2/1, V/V) solution.
Ultraviolet selectivity experiment adds 60uL fluorescent optical sensors 2 as shown in figure 4, take 3ml storing solutions to be placed in liquid cell, Survey its initial absorbance, be then respectively adding the various cation 60uL configured, measure its it is stable when absorbance.Observation figure 4 understand that compound 2 is to Fe3+Effect is obvious responsed to, occurs a new peak at 558nm, namely compound 2 is to Fe3+Have very Good selectivity.

Claims (5)

1. a kind of Fe3+Fluorescent optical sensor, it is characterised in that structure is as follows：
2.Fe3+The preparation method of fluorescent optical sensor, it is characterised in that comprise the following steps：
By rhodamine ethylenediamine and 1,1 '-thio-carbonyldiimidazole is dissolved in dichloromethane at normal temperatures, normal-temperature reaction 30-40min, After reaction is completed, removal of solvent under reduced pressure, extraction, silica gel post separation obtains the Fe3+Fluorescent optical sensor.
3. method as claimed in claim 2, it is characterised in that rhodamine ethylenediamine and 1,1 '-thio-carbonyldiimidazole rubs You are than being 1：1.
4. method as claimed in claim 2, it is characterised in that the eluent that silica gel post separation is used use volume ratio for MeOH：CH2Cl2=1：99 mixed liquor.
5. Fe as claimed in claim 13+Fluorescent optical sensor is in detection Fe3+On application.
CN201710333730.7A 2017-05-12 2017-05-12 Fe3+Fluorescent optical sensor, preparation method and applications Withdrawn CN107011351A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710333730.7A CN107011351A (en) 2017-05-12 2017-05-12 Fe3+Fluorescent optical sensor, preparation method and applications

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710333730.7A CN107011351A (en) 2017-05-12 2017-05-12 Fe3+Fluorescent optical sensor, preparation method and applications

Publications (1)

Publication Number Publication Date
CN107011351A true CN107011351A (en) 2017-08-04

Family

ID=59449223

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710333730.7A Withdrawn CN107011351A (en) 2017-05-12 2017-05-12 Fe3+Fluorescent optical sensor, preparation method and applications

Country Status (1)

Country Link
CN (1) CN107011351A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015139263A1 (en) * 2014-03-20 2015-09-24 The Procter & Gamble Company Stannous fluorescent probe
CN105884788A (en) * 2016-05-13 2016-08-24 南京理工大学 Fe<3+> molecular fluorescence sensor based on Rhodamine B and preparation method and application of Fe<3+> molecular fluorescence sensor
CN106047336A (en) * 2016-06-17 2016-10-26 南京理工大学 Fe<3+> molecular fluorescence sensor based on Rhodamine B as well as preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015139263A1 (en) * 2014-03-20 2015-09-24 The Procter & Gamble Company Stannous fluorescent probe
CN105884788A (en) * 2016-05-13 2016-08-24 南京理工大学 Fe<3+> molecular fluorescence sensor based on Rhodamine B and preparation method and application of Fe<3+> molecular fluorescence sensor
CN106047336A (en) * 2016-06-17 2016-10-26 南京理工大学 Fe<3+> molecular fluorescence sensor based on Rhodamine B as well as preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN104449675B (en) Cr &lt; 3+ &gt; sensor based on rhodamine B, preparation and application
CN105884788B (en) A kind of Fe3+ molecular fluorescences sensor based on rhodamine B, preparation method and application
Chao et al. A ratiometric fluorescence probe for monitoring cyanide ion in live cells
CN110590753B (en) Near-infrared SO of target mitochondria2Derivative ratiometric fluorescent probes and uses thereof
CN105295899B (en) Ratiometric fluorescent probe for detecting hydrogen sulfide and application of ratiometric fluorescent probe
CN107814808B (en) A kind of near-infrared response type two-photon fluorescence probe and its preparation method and application
CN111943907B (en) Fluorescent probe capable of simultaneously detecting TNT and TNP and preparation method thereof
CN105038761B (en) Fluorescence wavelength adjustable material and applications thereof
CN105924449A (en) Preparation and application for reaction type fluorescein fluorescent probe capable of detecting mercury ions
CN102827175A (en) N-(2,4-dinitrophenyl)-rhodamine B hydrazide and preparation method and application thereof
CN110229165A (en) Up-conversion fluorescence probe Rhodamine Derivatives and its application
CN103387830B (en) Chromium-ion ratio type fluorescence probe as well as preparation method and application thereof
CN107417693A (en) Rhodamine B luminescent material, preparation method and the application on fluorescence sense of the heterocycle containing furfural
CN104151867B (en) Temperature response type cyclodextrin probe double with pH and preparation method thereof
Fu et al. Target-activated and ratiometric photochromic probe for “double-check” detection of toxic thiols in live cells
CN106047336B (en) A kind of Fe based on rhodamine B3+Molecular fluorescence sensor, preparation method and application
CN108358882A (en) One type rhodamine compound and its preparation method and use
CN107235985B (en) A kind of fluorescence probe and the preparation method and application thereof detecting bivalent cupric ion
CN104087288A (en) Rhodamine B-based aluminum ion sensor, preparation and application
CN107021967B (en) Fe based on rhodamine B3+Fluorescent optical sensor, preparation method and application
Karakuş et al. Fluorescein based three-channel probe for the selective and sensitive detection of CO32− ions in an aqueous environment and real water samples
CN109053750B (en) Rhodamine hydrazine Schiff base derivative and preparation method and application thereof
CN108358938A (en) A kind of preparation method and applications of the rhodamine B luminescent material based on furoyl chloride
CN107011351A (en) Fe3+Fluorescent optical sensor, preparation method and applications
CN110483368A (en) A kind of fluorescence probe and preparation method thereof detecting mercury ion and application method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20170804