CN104262351B - The preparation method of N-(dinitrophenyl group)-rhodamine B hydrazides and the application of detection Cu (II) thereof - Google Patents
The preparation method of N-(dinitrophenyl group)-rhodamine B hydrazides and the application of detection Cu (II) thereof Download PDFInfo
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- 229940043267 rhodamine b Drugs 0.000 title claims abstract description 59
- 238000001514 detection method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 title abstract description 47
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000003287 optical effect Effects 0.000 claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 20
- -1 dinitrophenyl Chemical group 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 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 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 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 6
- 150000001875 compounds Chemical class 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 230000008033 biological extinction Effects 0.000 abstract description 9
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 abstract description 4
- 238000011896 sensitive detection Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 34
- 239000010949 copper Substances 0.000 description 17
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [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 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000010413 mother solution Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 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
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- YKYOUMDCQGMQQO-UHFFFAOYSA-L Cadmium chloride Inorganic materials Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000011636 chromium(III) chloride Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000013461 design Methods 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
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910001629 magnesium chloride 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
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000012271 agricultural production 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
- 238000004364 calculation method Methods 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
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 230000002068 genetic effect Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 210000002216 heart Anatomy 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
- 238000003018 immunoassay 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
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011265 semifinished product Substances 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
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000013518 transcription Methods 0.000 description 1
- 230000035897 transcription Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005747 tumor angiogenesis Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
- G01N21/17—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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- 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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- 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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Abstract
The invention discloses the preparation method of N-(dinitrophenyl group)-rhodamine B hydrazides and the application of detection Cu (II) thereof. The preparation method of N-(2,4-the dinitrophenyl)-rhodamine B hydrazides of the present invention, comprises the steps: to make rhodamine B acyl chlorides and 2,4 dinitrophenyl hydrazine react generation N-(2,4-dinitrophenyl)-rhodamine B hydrazides. N-(2,4-dinitrophenyl)-rhodamine B hydrazides itself, but can optionally and Cu without color and fluorescence2+Ion occurs colour developing and fluorescence to open reaction, colourless material generate the system of excellent optical performance, substantially increase Cu2+The detection sensitivity of ion and selectivity. Therefore, N-(2,4-dinitrophenyl)-rhodamine B hydrazides is applicable to Cu2+Ion carries out high selectivity and highly sensitive detection, and this detection can be undertaken by extinction spectrum and two kinds of methods of fluorescence spectrum.
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-(dinitrophenyl group)-rhodamine B hydrazides and preparation method thereof and application ".
Technical field
The present invention relates to the preparation method of N-(dinitrophenyl group)-rhodamine B hydrazides and the application of detection Cu (II) thereof.
Background technology
Heavy metal and transition metal are present in nature widely, some of which element has very important function in life process, as tumor angiogenesis factor is played the various important life processes such as important adjustment effect, zinc wide participation cell development, genetic transcription, neurotransmission by copper; Biology is then had extremely strong toxicity by other element when low concentration, as lead can cause the pathological changes of digestive system, nervous system and heart. Therefore, set up heavy metal and transition metal detection method fast and efficiently all to have great importance in life sciences, environmental science, medical science and agricultural 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, high selectivity and the features such as organism Non-Destructive Testing can being realized based on ion induction, show one's talent from numerous detection meanss, show wide application prospect in fields such as metal ion detection, fluorescence immunoassay and cell imagings. The optical pickocff of function admirable is the foundation stone constructing and developing above-mentioned field applied research. Although there are reports to can be used for the optical pickocff of copper ion identification, as Chereddy et al. (DyesandPigments, 2011,91 (3): 378-382) reports a kind of Cu containing double; two rhodamine B groups2+Optical pickocff; Swamy et al. (ChemicalCommunications, 2008,45:5915-5917) constructs the Cu of a kind of single boric acid-rhodamine B conjugation2+Optical pickocff, but its sensitivity is slightly worse, is adding 100 times of centinormal 1 Cu2+Time, fluorescence intensity only improves 6.4 times;Kaur et al. (ChemicalCommunications, 2002,2840-2841) has synthesized a kind of Cu containing anthryl group2+Optical pickocff, but absorption and transmitting wavelength are shorter, it is easy to form interference; Yu et al. (Chemistry-AEuropeanJournal, 2008,14 (23): 6892-6900) reports a kind of Fluorescence Increasing type Cu2+Optical pickocff, but Cu cannot significantly be distinguished by this sensor2+And Hg2+��
Therefore, design synthesis has the selective Cu of long wavelength, high sensitivity and height2+Optical pickocff still suffers from 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. With rhodamine for parent, modify with special reactive group, just the high selective binding of the long wavelength of rhodamine, high sensitivity and specific groups can be got up, obtain excellent metal ion analysis reagent, analysis method can also be extended to fluorimetry from absorption photometry, expands the scope of application.
Summary of the invention
It is an object of the present invention to provide one can optical pickocff molecule N-(the dinitrophenyl group)-rhodamine B hydrazides of high selectivity and high-sensitivity detection Cu (II).
N-provided by the present invention (dinitrophenyl group)-rhodamine B hydrazides (N-(2,4-dinitrophenyl) rhodamineB-hydrazide; It is abbreviated as: DNPRH), its structure such as Formulas I,
This optical pickocff molecule N-(dinitrophenyl group)-rhodamine B hydrazides is made up of three parts: rhodamine B is as fluorescent parent; Diazanyl is as bridging agent; Meta-dinitro-benzent is as response group.
Preparation N-(2 provided by the present invention, 4-dinitrophenyl) method of-rhodamine B hydrazides, comprise the steps: to make rhodamine B acyl chlorides and 2,4 dinitrophenyl hydrazine react generation N-(2,4-dinitrophenyl)-rhodamine B hydrazides.
Wherein, rhodamine B acyl chlorides and 2,4 dinitrophenyl hydrazine is made to react as will the acetonitrile solution of the acetonitrile solution dropwise of rhodamine B acyl chlorides to 2,4 dinitrophenyl hydrazine and triethylamine react 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 response time is 6 hours.
It is a further object to provide the purposes of N-(dinitrophenyl group)-rhodamine B hydrazides.
Purposes provided by the present invention is following 1)-7) at least one:
1) fluorescent probe being made up of N-(dinitrophenyl group)-rhodamine B hydrazides;
2) N-(dinitrophenyl group)-rhodamine B hydrazides is as fluorescent probe or as detection Cu2+Fluorescent probe in application;
3) optical pickocff containing N-(dinitrophenyl group)-rhodamine B hydrazides;
4) N-(dinitrophenyl group)-rhodamine B hydrazides is preparing optical pickocff or detection Cu2+Optical pickocff in application;
5) N-(dinitrophenyl group)-rhodamine B hydrazides is at detection Cu2+Application in ion;
6) fluorescent probe above-mentioned 1) is at detection Cu2+Application in ion;
7) optical pickocff above-mentioned 3) is at detection Cu2+Application in ion.
Wherein, 1) described fluorescent probe and 3) described optical pickocff be used equally to detection Cu2+��
Inventor experiments prove that, N-(2,4-dinitrophenyl)-rhodamine B hydrazides itself, but can optionally and Cu without color and fluorescence2+Ion occurs colour developing and fluorescence to open reaction, colourless material generate the system of excellent optical performance, substantially increase Cu2+The detection sensitivity of ion and selectivity.Therefore, N-(2,4-dinitrophenyl)-rhodamine B hydrazides is applicable to Cu2+Ion carries out high selectivity and highly sensitive detection, and this detection can be undertaken by extinction spectrum and two kinds of methods of fluorescence spectrum.
When N-(2,4-dinitrophenyl)-rhodamine B hydrazides is as detectable, highly sensitive, Cu2+Ion concentration, on 1 ��M, adopts absorption spectroanalysis method just can detect and obtains; When adopting fluorescence spectrum analysing method, Cu2+Ion concentration also is able to produce obvious fluorescence response at 1 ��M equally. It addition, N-(2,4-dinitrophenyl)-rhodamine B hydrazides and Cu2+The absorption of ion and fluorescence response have significantly high selectivity, K+��Na+��Ag+��Ca2+��Mg2+��Al3+��Fe3+��Fe2+��Pb2+��Zn2+��Hg2+��Cd2+��Cr3+And Ni2+Deng common ion to Cu2+Mensuration almost without interference, therefore can get rid of the interference to testing result of numerous interfering ion, detection specificity is high. It addition, application N-(2,4-dinitrophenyl)-rhodamine B hydrazides is to Cu2+When ion detects, owing to detection sensitivity is high, it is only necessary to namely the sample of trace can complete, and has widened the range of application of the method.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of N-(dinitrophenyl group)-rhodamine B hydrazides.
Fig. 2 is the nmr spectrum of N-(dinitrophenyl group)-rhodamine B hydrazides.
Fig. 3 is Cu2+The graph of a relation of the reaction system absorption spectrum of concentration and N-(dinitrophenyl group)-rhodamine B hydrazides.
Fig. 4 is Cu2+With various interference reagent, the absorption spectrum of N-(dinitrophenyl group)-rhodamine B hydrazides is affected comparison figure.
Fig. 5 is Cu2+The graph of a relation of the reaction system fluorescence spectrum of concentration and N-(dinitrophenyl group)-rhodamine B hydrazides.
Fig. 6 is Cu2+With various interference reagent, the fluorescence spectrum of N-(dinitrophenyl group)-rhodamine B hydrazides is affected comparison figure.
Detailed description of the invention
Below example is easy to be more fully understood that the present invention, but does not limit the present invention. Experimental technique in following embodiment, if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all commercially obtain.
The preparation of embodiment 1, optical pickocff molecule N-(dinitrophenyl group)-rhodamine B hydrazides (DNPRH)
Reaction process is as it is shown in figure 1, concrete grammar is as follows: be dissolved in 10mL1,2-dichloroethanes by rhodamine B (formula II, 400.0mg, 0.90mmol), slowly drips 0.8mL phosphorus oxychloride wherein. This mixed system is under agitation heated to reflux 4h, and then decompression boils off solvent, obtains the rhodamine B acyl chlorides (formula III) of aubergine oily. This acyl chlorides semifinished product, without purification, is directly added into 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 30mL2,4-dinitrophenylhydrazine (0.60g, 3.0mmol) and triethylamine (1.6mL, 11.6mmol). Continuing stirring 6h under room temperature (20-25 DEG C), decompression boils off solvent and obtains aubergine grease. By silica gel chromatographic column, this oily mixture is easily separated purification, and leacheate is petroleum ether (60��90 DEG C)/ethyl acetate (5:1, v/v). Finally obtaining 330mg product N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH), productivity is 58.6%.
Elementary analysis (the C of N-(dinitrophenyl group)-rhodamine B hydrazides (DNPRH)34H34N6O6) value of calculation: C65.58, H5.50, N13.50%; Measured value: C65.14, H5.38, N13.76%.
The nuclear-magnetism qualification result of N-(dinitrophenyl group)-rhodamine B hydrazides (DNPRH): 1HNMR (600MHz, CD3CN, 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 Fig. 2 such as. INSTRUMENT MODEL: VarianNMRSystem600M.
Embodiment 2, N-(dinitrophenyl group)-rhodamine B hydrazides (DNPRH) as analytical reagent to Cu2+Carry out extinction detection
1, N-(dinitrophenyl group)-rhodamine B hydrazides is to Cu2+Carry out the sensitivity of extinction detection
The alcoholic solution (concentration 1mM) of 500 �� L reagent Ns-(2,4-dinitrophenyl)-rhodamine B hydrazides is joined in 50mL volumetric flask, with ethanol constant volume to 50mL, uses (concentration 10 ��Ms) as mother solution diluent. Take above-mentioned mother solution diluent 3mL respectively, add the Cu of proper volume2+Storing solution (CuCl2Solution) (concentration 1mM), make Cu in system2+Concentration respectively 1��15 ��M (Concentraton gradient is 1 ��M). After reacting 40min under room temperature (20-25 DEG C), transfer 3mL reactant liquor is in 1cm quartz colorimetric utensil, using ethanol as blank, measures ultra-violet absorption spectrum. Fig. 3 is Cu2+The graph of a relation of concentration and reaction system absorption spectrum (embeds figure: 556nm place reaction system absorbance and Cu2+The linear relationship of concentration). As it is shown on figure 3, the maximum absorption wavelength of reaction system is at 556nm; Further, along with Cu2+The raising of concentration, the absorbance of reaction system is gradually increased, and is finally reached a platform. Cu in figure2+Concentration is respectively as follows: 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14 and 15 ��Ms, and the range of linearity is 1��10 ��M, 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 standard curve-9M, i.e. 0.46ug/L. Result above shows, analytical reagent N-(2,4-dinitrophenyl)-rhodamine B hydrazides is capable of Cu2+High sensitivity extinction detection.
2, N-(dinitrophenyl group)-rhodamine B hydrazides is to Cu2+Carry out the specificity of extinction detection
Take several test tubes simultaneously, carry out operation similar to the above, simply will add Cu2+Become addition various interfering ions (concentration is all 20 ��Ms), do not produce obvious extinction response, illustrate N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH) as analytical reagent to Cu2+Having high selectivity when carrying out extinction detection, result is shown in Fig. 4. Wherein K+Thered is provided by KAC solution, Na+Thered is provided by NaAC solution, Ag+By AgNO3Solution provides, Mg2+By MgCl2Solution provides, Ca2+By CaCl2Solution provides, Al3+By AlCl3Solution provides, Fe2+By FeCl2There is provided, Fe3+By FeCl3There is provided, Pb2+By Pb (AC)2Solution provides, Zn2+By Zn (AC)2Solution provides, Hg2+By HgCl2Solution provides, Cd2+By CdCl2Solution provides, Cr3+By CrCl3Solution provides, Ni2+By Ni (AC)2Solution provides.
Embodiment 3, N-(dinitrophenyl group)-rhodamine B hydrazides (DNPRH) as analytical reagent to Cu2+Carry out fluoroscopic examination
1, N-(dinitrophenyl group)-rhodamine B hydrazides is to Cu2+Carry out the sensitivity of fluoroscopic examination
The alcoholic solution (concentration 1mM) of 500 �� L reagent Ns-(2,4-dinitrophenyl)-rhodamine B hydrazides is joined in 50mL volumetric flask, with ethanol constant volume to 50mL, uses (concentration 10 ��Ms) as mother solution diluent. Take above-mentioned mother solution diluent 3mL respectively, add the Cu of proper volume2+Storing solution (CuCl2Solution) (concentration 1mM), make Cu in system2+Concentration respectively 1��15 ��M (Concentraton gradient is 1 ��M). The fluorescence spectrum of assaying reaction system after reaction 40min under room temperature (20-25 DEG C).
Fig. 5 is Cu2+Graph of a relation (reaction system fluorescence intensity and the Cu of concentration and reaction system fluorescence spectrum2+The linear relationship of concentration, ��ex/em=520/578nm).The exciting and launch wavelength respectively 520 and 578nm of system; Along with Cu2+The raising of concentration, the fluorescence intensity of reaction system is gradually increased, and is finally reached a platform. Cu in Fig. 52+Concentration is respectively as follows: 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14 and 15 ��Ms, and the range of linearity is 5��12 ��Ms, 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 standard curve-9M, i.e. 0.07ug/L. Result above shows, analytical reagent N-(2,4-dinitrophenyl)-rhodamine B hydrazides is capable of Cu2+Highly sensitive fluoroscopic examination.
2, N-(dinitrophenyl group)-rhodamine B hydrazides is to Cu2+Carry out the specificity of fluoroscopic examination
Take several test tubes simultaneously, carry out operation similar to the above, simply will add Cu2+Become addition various interfering ions (concentration is all 20 ��Ms), do not produce obvious fluorescence response, illustrate N-(2,4-dinitrophenyl)-rhodamine B hydrazides (DNPRH) as analytical reagent to Cu2+Having high selectivity when carrying out fluoroscopic examination, result is shown in Fig. 6. Wherein K+Thered is provided by KAC solution, Na+Thered is provided by NaAC solution, Ag+By AgNO3Solution provides, Mg2+By MgCl2Solution provides, Ca2+By CaCl2Solution provides, Al3+By AlCl3Solution provides, Fe2+By FeCl2There is provided, Fe3+By FeCl3There is provided, Pb2+By Pb (AC)2Solution provides, Zn2+By Zn (AC)2Solution provides, Hg2+By HgCl2Solution provides, Cd2+By CdCl2Solution provides, Cr3+By CrCl3Solution provides, Ni2+By Ni (AC)2Solution provides.
Claims (7)
1. the preparation method of compound of formula I, comprises the steps: to make rhodamine B acyl chlorides and 2,4 dinitrophenyl hydrazine react production I:
2. method according to claim 1, it is characterised in that: described in make rhodamine B acyl chlorides and 2,4 dinitrophenyl hydrazine react as will the acetonitrile solution of the acetonitrile solution dropwise of rhodamine B acyl chlorides to 2,4 dinitrophenyl hydrazine and triethylamine react.
3. the compound of formula I described in claim 1 is as detection Cu2+Fluorescent probe in application.
4. optical pickocff, it is characterised in that: described optical pickocff contains the compound of formula I described in claim 1.
5. the compound of formula I described in claim 1 is at preparation detection Cu2+Optical pickocff in application.
6. the compound of formula I described in claim 1 is at detection Cu2+Application in ion.
7. the optical pickocff described in claim 4 is at detection Cu2+Application in ion.
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