CN104262351A - A preparing method of N-(2,4-dinitrophenyl)rhodamine B-hydrazide and an application of the N-(2,4-dinitrophenyl)rhodamine B-hydrazide for detection of Cu(II) - Google Patents
A preparing method of N-(2,4-dinitrophenyl)rhodamine B-hydrazide and an application of the N-(2,4-dinitrophenyl)rhodamine B-hydrazide for detection of Cu(II) Download PDFInfo
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- CN104262351A CN104262351A CN201410418089.3A CN201410418089A CN104262351A CN 104262351 A CN104262351 A CN 104262351A CN 201410418089 A CN201410418089 A CN 201410418089A CN 104262351 A CN104262351 A CN 104262351A
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- rhodamine
- dinitrophenyl
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- hydrazide
- hydrazides
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- 238000001514 detection method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 16
- WTDHTIVYKKLOTC-UHFFFAOYSA-N 2-amino-3',6'-bis(diethylamino)spiro[isoindole-3,9'-xanthene]-1-one Chemical compound NN1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 WTDHTIVYKKLOTC-UHFFFAOYSA-N 0.000 title abstract description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title abstract description 3
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 52
- 230000003287 optical effect Effects 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007850 fluorescent dye Substances 0.000 claims description 11
- -1 rhodamine B acyl chlorides Chemical class 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000000862 absorption spectrum Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 53
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 41
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 230000008033 biological extinction Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000002870 angiogenesis inducing agent Substances 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000005062 synaptic transmission Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000013518 transcription Methods 0.000 description 1
- 230000035897 transcription Effects 0.000 description 1
- 230000005747 tumor angiogenesis Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- 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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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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
- 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
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- Biochemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
A preparing method of N-(2,4-dinitrophenyl)rhodamine B-hydrazide and an application of the N-(2,4-dinitrophenyl)rhodamine B-hydrazide for detection of Cu(II) are disclosed. The preparing method includes a step of reacting rhodamine B acid chloride and 2,4-dinitrophenylhydrazine to generate the N-(2,4-dinitrophenyl)rhodamine B-hydrazide. The N-(2,4-dinitrophenyl)rhodamine B-hydrazide itself is free of color and fluorescence, but can generate coloring and fluorescence generating reactions selectively with Cu<2+>, so that a colorless substance is turned into a system with excellent optical properties, and detection sensitivity and selectivity for the Cu<2+> are largely enhanced. Accordingly, the N-(2,4-dinitrophenyl)rhodamine B-hydrazide is suitable for high-selectivity and high-sensitivity detection of the Cu<2+>. The detection can be performed by a light absorption spectrum method and a fluorescence spectrum method.
Description
The divisional application that the application is application number is 201210323481.0, the applying date is on 09 04th, 2012, invention and created name is " N-(2,4-dinitrophenyl)-rhodamine B hydrazides and preparation method thereof and application ".
Technical field
The present invention relates to the preparation method of N-(2,4-dinitrophenyl)-rhodamine B hydrazides and detect the application of Cu (II).
Background technology
Heavy metal and transition metal are present in occurring in nature widely, some elements wherein have very important function in vital process, as copper plays important regulating effect to tumor angiogenesis factor, the various important vital processes such as zinc wide participation cell development, genetic transcription, neurotransmission; Other element then has extremely strong toxicity when low concentration to biology, as lead can cause the pathology of Digestive tract, neural system and heart.Therefore, set up heavy metal and transition metal detection method fast and efficiently all to have great importance in life science, environmental science, medical science and agriculture production etc.
In recent years, the optical sensor technology of optical signalling change mechanism identification metal ion is produced owing to there is high sensitivity, highly selective and the features such as organism nondestructive testing can being realized based on ion induction, show one's talent from numerous detection means, show wide application prospect in fields such as metal ion detection, fluoroimmunoassay and cell imagings.The optical pickocff of excellent property is the foundation stone constructing and develop the applied research of above-mentioned field.Although there are reports to can be used for the optical pickocff of cupric ion identification, as the people such as Chereddy (Dyes and Pigments, 2011,91 (3): 378-382) report a kind of Cu containing two rhodamine B group
2+optical pickocff; The people such as Swamy (Chemical Communications, 2008,45:5915-5917) construct a kind of Cu of single boric acid-rhodamine B conjugation
2+optical pickocff, but its sensitivity is slightly poor, is adding 100 times of centinormal 1 Cu
2+time, fluorescence intensity only improves 6.4 times; The people such as Kaur (Chemical Communications, 2002,2840-2841) have synthesized a kind of Cu containing anthryl group
2+optical pickocff, but absorb and emission wavelength shorter, easily form interference; The people such as Yu (Chemistry-A European Journal, 2008,14 (23): 6892-6900) report a kind of Fluorescence Increasing type Cu
2+optical pickocff, but this sensor significantly cannot distinguish Cu
2+and Hg
2+.
Therefore, design and synthesis has the Cu of long wavelength, highly sensitive and highly selective
2+optical pickocff still faces lot of challenges.As a kind of important optical material, dye stuff of rhodamine kinds is widely used in design and the synthesis (J.Am.Chem.Soc.1997,119:7386-7387) of various analytical reagent because of its excellent extinction and fluorescent characteristic.Take rhodamine as parent, modify with special reactive group, just the highly selective of the long wavelength of rhodamine, highly sensitive and specific groups can be combined, obtain excellent metal ion analysis reagent, analytical procedure also can be extended to fluorimetry from absorption photometry, the scope of broadened application.
Summary of the invention
An object of the present invention is to provide one can optical pickocff molecule-N-(2,4-the dinitrophenyl)-rhodamine B hydrazides of highly selective and high-sensitivity detection Cu (II).
N-provided by the present invention (2,4-dinitrophenyl)-rhodamine B hydrazides (N-(2,4-dinitrophenyl) rhodamine B-hydrazide; Be abbreviated as: DNPRH), its structure such as formula I,
This optical pickocff molecule N-(2,4-dinitrophenyl)-rhodamine B hydrazides is made up of three parts: rhodamine B is as fluorescent parent; Diazanyl is as bridging agent; Meta-dinitrobenzene is group responsively.
Preparation N-(2 provided by the present invention, 4-dinitrophenyl) method of-rhodamine B hydrazides, comprise the steps: that making rhodamine B acyl chlorides and 2,4 dinitrophenyl hydrazine carry out reaction generates N-(2,4-dinitrophenyl)-rhodamine B hydrazides.
Wherein, rhodamine B acyl chlorides and 2,4 dinitrophenyl hydrazine is made to carry out reacting for being reacted in the acetonitrile solution of 2,4 dinitrophenyl hydrazine and triethylamine by the acetonitrile solution dropwise of rhodamine B acyl chlorides described in.In described reaction, the mol ratio of rhodamine B acyl chlorides, 2,4 dinitrophenyl hydrazine and triethylamine can be 9:30:116.The temperature of described reaction is room temperature (20-25 DEG C), and the reaction times is 6 hours.
Another object of the present invention is to provide the purposes of N-(2,4-dinitrophenyl)-rhodamine B hydrazides.
Purposes provided by the present invention is following 1)-7) at least one:
1) fluorescent probe be made up of N-(2,4-dinitrophenyl)-rhodamine B hydrazides;
2) N-(2,4-dinitrophenyl)-rhodamine B hydrazides is detecting Cu as fluorescent probe or conduct
2+fluorescent probe in application;
3) optical pickocff containing N-(2,4-dinitrophenyl)-rhodamine B hydrazides;
4) N-(2,4-dinitrophenyl)-rhodamine B hydrazides is being prepared optical pickocff or is detecting Cu
2+optical pickocff in application;
5) N-(2,4-dinitrophenyl)-rhodamine B hydrazides is at detection Cu
2+application in ion;
6) fluorescent probe above-mentioned 1) is at detection Cu
2+application in ion;
7) optical pickocff above-mentioned 3) is at detection Cu
2+application in ion.
Wherein, 1) described fluorescent probe and 3) described optical pickocff all can be used for detect Cu
2+.
Inventor confirms by experiment, N-(2,4-dinitrophenyl)-rhodamine B hydrazides itself without color and fluorescence, but can optionally with Cu
2+there is colour developing in ion and fluorescence opens reaction, generated the system of excellent optical performance, substantially increase Cu by colourless material
2+the detection sensitivity of ion and selectivity.Therefore, N-(2,4-dinitrophenyl)-rhodamine B hydrazides is applicable to Cu
2+ion carries out highly selective and highly sensitive detection, and this detection can be undertaken by extinction spectrum and fluorescence spectrum two kinds of methods.
When N-(2,4-dinitrophenyl)-rhodamine B hydrazides is as detection reagent, highly sensitive, Cu
2+ionic concn, on 1 μM, adopts absorption spectroanalysis method just can detect and obtains; When adopting fluorescence spectrum analysing method, Cu
2+ionic concn equally also can produce obvious fluorescence response at 1 μM.In addition, N-(2,4-dinitrophenyl)-rhodamine B hydrazides and Cu
2+the Absorption and fluorescence response of ion has very high selectivity, K
+, Na
+, Ag
+, Ca
2+, Mg
2+, Al
3+, Fe
3+, Fe
2+, Pb
2+, Zn
2+, Hg
2+, Cd
2+, Cr
3+and Ni
2+deng common ion to Cu
2+mensuration almost do not disturb, therefore can get rid of the interference of numerous interfering ion to detected result, detection specificity is high.In addition, N-(2,4-dinitrophenyl)-rhodamine B hydrazides is applied to Cu
2+when ion detects, because detection sensitivity is high, only need the sample of trace namely can complete, widened the range of application of the method.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of N-(2,4-dinitrophenyl)-rhodamine B hydrazides.
Fig. 2 is the nmr spectrum of N-(2,4-dinitrophenyl)-rhodamine B hydrazides.
Fig. 3 is Cu
2+the graph of a relation of the reaction system absorption spectrum of concentration and N-(2,4-dinitrophenyl)-rhodamine B hydrazides.
Fig. 4 is Cu
2+with the absorption spectrum impact contrast figure of various interference reagent to N-(2,4-dinitrophenyl)-rhodamine B hydrazides.
Fig. 5 is Cu
2+the graph of a relation of the reaction system fluorescence spectrum of concentration and N-(2,4-dinitrophenyl)-rhodamine B hydrazides.
Fig. 6 is Cu
2+with the fluorescence spectrum impact contrast figure of various interference reagent to N-(2,4-dinitrophenyl)-rhodamine B hydrazides.
Embodiment
Following embodiment is convenient to understand the present invention better, but does not limit the present invention.Experimental technique in following embodiment, if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, optical pickocff molecule N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH)
As shown in Figure 1, concrete grammar is as follows for reaction process: be dissolved in 10mL 1,2-ethylene dichloride by rhodamine B (formula II, 400.0mg, 0.90mmol), slowly drips 0.8mL phosphorus oxychloride wherein.This mixed system under agitation reflux 4h, then pressure reducing and steaming solvent, obtain the rhodamine B acyl chlorides (formula III) of red-purple oily.This acyl chlorides raw product, without purifying, directly adds 10mL acetonitrile and forms solution.Then, under room temperature (20-25 DEG C), in 30min, this dropwise is added drop-wise in the acetonitrile solution of 30mL 2,4 dinitrophenyl hydrazine (0.60g, 3.0mmol) and triethylamine (1.6mL, 11.6mmol).Continue under room temperature (20-25 DEG C) to stir 6h, pressure reducing and steaming solvent obtains red-purple oily matter.This oily mixture is carried out separation and purification by silica gel chromatographic column, and leacheate is sherwood oil (60 ~ 90 DEG C)/ethyl acetate (5:1, v/v).Finally obtain 330mg product N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH), productive rate is 58.6%.
Ultimate analysis (the C of N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH)
34h
34n
6o
6) calculated value: C 65.58, H 5.50, N 13.50%; Measured value: C 65.14, H 5.38, N 13.76%.
The nuclear-magnetism qualification result of N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH): 1H NMR (600MHz, CD
3cN, 298K): 8.82 (s, 1H), 8.80 (d, 1H), 7.99 (d, 1H), 7.90 (dd, 1H), 7.75 (t, 1H), 7.69 (t, 1H), 7.30 (d, 1H), 6.82 (d, 1H), 6.41 (m, 6H), 3.31 (s, 8H), 1.08 (s, 12H).Nuclear magnetic spectrum is as Fig. 2.INSTRUMENT MODEL: Varian NMR System 600M.
Embodiment 2, N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH) as analytical reagent to Cu
2+carry out extinction detection
1, N-(2,4-dinitrophenyl)-rhodamine B hydrazides is to Cu
2+carry out the sensitivity of extinction detection
The ethanolic soln (concentration 1mM) of 500 μ L reagent-N-(2,4-dinitrophenyl)-rhodamine B hydrazides is joined in 50mL volumetric flask, with ethanol constant volume to 50mL, uses (concentration 10 μMs) as mother liquor diluent.Get above-mentioned mother liquor diluent 3mL respectively, add the Cu of proper volume
2+storing solution (CuCl
2solution) (concentration 1mM), make Cu in system
2+concentration is respectively 1 ~ 15 μM (concentration gradient is 1 μM).Shift 3mL reaction solution after reacting 40min under room temperature (20-25 DEG C) in 1cm quartz colorimetric utensil, using ethanol as blank, measure ultra-violet absorption spectrum.Fig. 3 is Cu
2+the graph of a relation of concentration and reaction system absorption spectrum (embeds and schemes: 556nm place reaction system absorbancy and Cu
2+the linear relationship of concentration).As shown in Figure 3, the maximum absorption wavelength of reaction system is at 556nm; Further, along with Cu
2+the raising of concentration, the absorbancy of reaction system increases gradually, and finally reaches a platform.Cu in figure
2+concentration is respectively: 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14 and 15 μM, and linearity range is 1 ~ 10 μM, and the detection limit of method is calculated as 7.3 × 10 with the standard deviation of the blank signal of 3 times divided by the slope of typical curve
-9m, i.e. 0.46ug/L.Above result shows, analytical reagent-N-(2,4-dinitrophenyl)-rhodamine B hydrazides can realize Cu
2+highly sensitive extinction detect.
2, N-(2,4-dinitrophenyl)-rhodamine B hydrazides is to Cu
2+carry out the specificity of extinction detection
Get several test tubes simultaneously, carry out similar operation above, just will add Cu
2+become and add various interfering ion (concentration is all 20 μMs), do not produce the response of obvious extinction, N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH) is described as analytical reagent to Cu
2+carry out, when extinction detects, there is high selectivity, the results are shown in Figure 4.Wherein K
+thered is provided by KAC solution, Na
+thered is provided by NaAC solution, Ag
+by AgNO
3solution provides, Mg
2+by MgCl
2solution provides, Ca
2+by CaCl
2solution provides, Al
3+by AlCl
3solution provides, Fe
2+by FeCl
2there is provided, Fe
3+by FeCl
3there is provided, Pb
2+by Pb (AC)
2solution provides, Zn
2+by Zn (AC)
2solution provides, Hg
2+by HgCl
2solution provides, Cd
2+by CdCl
2solution provides, Cr
3+by CrCl
3solution provides, Ni
2+by Ni (AC)
2solution provides.
Embodiment 3, N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH) as analytical reagent to Cu
2+carry out fluoroscopic examination
1, N-(2,4-dinitrophenyl)-rhodamine B hydrazides is to Cu
2+carry out the sensitivity of fluoroscopic examination
The ethanolic soln (concentration 1mM) of 500 μ L reagent-N-(2,4-dinitrophenyl)-rhodamine B hydrazides is joined in 50mL volumetric flask, with ethanol constant volume to 50mL, uses (concentration 10 μMs) as mother liquor diluent.Get above-mentioned mother liquor diluent 3mL respectively, add the Cu of proper volume
2+storing solution (CuCl
2solution) (concentration 1mM), make Cu in system
2+concentration is respectively 1 ~ 15 μM (concentration gradient is 1 μM).The fluorescence spectrum of assaying reaction system after 40min is reacted under room temperature (20-25 DEG C).
Fig. 5 is Cu
2+graph of a relation (reaction system fluorescence intensity and the Cu of concentration and reaction system fluorescence spectrum
2+the linear relationship of concentration, λ
ex/em=520/578nm).Exciting of system is respectively 520 and 578nm with emission wavelength; Along with Cu
2+the raising of concentration, the fluorescence intensity of reaction system increases gradually, and finally reaches a platform.Cu in Fig. 5
2+concentration is respectively: 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14 and 15 μM, and linearity range is 5 ~ 12 μMs, and the detection limit of method is calculated as 1.1 × 10 with the standard deviation of the blank signal of 3 times divided by the slope of typical curve
-9m, i.e. 0.07ug/L.Above result shows, analytical reagent-N-(2,4-dinitrophenyl)-rhodamine B hydrazides can realize Cu
2+highly sensitive fluoroscopic examination.
2, N-(2,4-dinitrophenyl)-rhodamine B hydrazides is to Cu
2+carry out the specificity of fluoroscopic examination
Get several test tubes simultaneously, carry out similar operation above, just will add Cu
2+become and add various interfering ion (concentration is all 20 μMs), do not produce obvious fluorescence response, N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH) is described as analytical reagent to Cu
2+when carrying out fluoroscopic examination, there is high selectivity, the results are shown in Figure 6.Wherein K
+thered is provided by KAC solution, Na
+thered is provided by NaAC solution, Ag
+by AgNO
3solution provides, Mg
2+by MgCl
2solution provides, Ca
2+by CaCl
2solution provides, Al
3+by AlCl
3solution provides, Fe
2+by FeCl
2there is provided, Fe
3+by FeCl
3there is provided, Pb
2+by Pb (AC)
2solution provides, Zn
2+by Zn (AC)
2solution provides, Hg
2+by HgCl
2solution provides, Cd
2+by CdCl
2solution provides, Cr
3+by CrCl
3solution provides, Ni
2+by Ni (AC)
2solution provides.
Claims (8)
1. the preparation method of formula I, comprises the steps: to make rhodamine B acyl chlorides and 2,4 dinitrophenyl hydrazine carry out reaction production I:
2. method according to claim 1, is characterized in that: described in make rhodamine B acyl chlorides and 2,4 dinitrophenyl hydrazine carry out reacting for being reacted in the acetonitrile solution of 2,4 dinitrophenyl hydrazine and triethylamine by the acetonitrile solution dropwise of rhodamine B acyl chlorides.
3. fluorescent probe, is characterized in that: described fluorescent probe is formula I according to claim 1, and described fluorescent probe is for detecting Cu
2+.
4. formula I according to claim 1 is detecting Cu as fluorescent probe or conduct
2+fluorescent probe in application.
5. optical pickocff, is characterized in that: described optical pickocff contains formula I according to claim 1.
6. optical pickocff according to claim 5, is characterized in that: described optical pickocff is for detecting Cu
2+.
7. formula I according to claim 1 is being prepared optical pickocff or is detecting Cu
2+optical pickocff in application.
8. formula I according to claim 1, fluorescent probe according to claim 3, optical pickocff described in claim 5 or 6 are at detection Cu
2+application in ion.
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| CN105199715A (en) * | 2015-10-13 | 2015-12-30 | 河南理工大学 | Fluorescence probe based on rhodamine B derivative as well as preparation method and application thereof |
| CN107219206A (en) * | 2017-06-28 | 2017-09-29 | 苏州浪声科学仪器有限公司 | A kind of analysis method of content of copper ion |
| CN107501285A (en) * | 2017-09-08 | 2017-12-22 | 中国地质大学（武汉） | A kind of water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification and preparation method, application |
| CN111551544A (en) * | 2020-05-06 | 2020-08-18 | 东南大学 | Bivalent copper ion rapid detection device and detection method based on paper-based micro-fluidic chip |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105199715A (en) * | 2015-10-13 | 2015-12-30 | 河南理工大学 | Fluorescence probe based on rhodamine B derivative as well as preparation method and application thereof |
| CN107219206A (en) * | 2017-06-28 | 2017-09-29 | 苏州浪声科学仪器有限公司 | A kind of analysis method of content of copper ion |
| CN107501285A (en) * | 2017-09-08 | 2017-12-22 | 中国地质大学（武汉） | A kind of water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification and preparation method, application |
| CN111551544A (en) * | 2020-05-06 | 2020-08-18 | 东南大学 | Bivalent copper ion rapid detection device and detection method based on paper-based micro-fluidic chip |
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