CN105838352B - A kind of synthetic method of probe of the Visual retrieval mercury ion based on chromene nitrile and application - Google Patents

A kind of synthetic method of probe of the Visual retrieval mercury ion based on chromene nitrile and application Download PDF

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CN105838352B
CN105838352B CN201610115917.5A CN201610115917A CN105838352B CN 105838352 B CN105838352 B CN 105838352B CN 201610115917 A CN201610115917 A CN 201610115917A CN 105838352 B CN105838352 B CN 105838352B
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probe
mercury ion
synthetic method
chromene
visual retrieval
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CN105838352A (en
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刘晓磊
杨小凤
孙国新
彭修静
曹胜光
崔玉
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University of Jinan
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    • C07—ORGANIC CHEMISTRY
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    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
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    • 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
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    • G01N21/6447—Fluorescence; Phosphorescence by visual observation
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Abstract

The invention discloses a kind of synthetic method of probe of Visual retrieval mercury ion and application, specially a kind of preparation of the trans subunit malononitrile of 2 (2 (4 ethyleneoxy) styryl) chromene 4, and the method for detecting mercury ion in the aqueous solution.The beneficial effects of the present invention are involved mercury ion probe building-up process is simple, reaction condition is gentle, yield is high, easy purification, and high sensitivity and selectivity are shown to mercury ion.The probe is in ethanol or in acetonitrile solvent faint yellow, after adding mercury ion, is changed into aubergine under alkalescence condition, and bore hole is visible, therefore can pass through the presence that color change indicates mercury ion in the aqueous solution.This method is simple to operate, cheap, has important actual application value in fields such as environmental sciences.

Description

A kind of synthetic method of the probe of the Visual retrieval mercury ion based on chromene nitrile And application
Technical field
The present invention relates to chemosynthesis technical field and heavy metal analysis field, and in particular to one kind is based on benzo pyrrole Mutter nitrile Visual retrieval mercury ion probe synthetic method and application.
Background technology
The widely using in modern humans' activity because of mercury and mercury compound, cause mercury pollution to turn into one and global ask Topic.Mercury ion can be converted into lipophilic organic mercury in natural environment, can be enriched with by food chain in human body, can cause Central nervous system and other organ damages.Therefore, design and synthesize effectively identification mercury ion probe for environmental science with The subjects such as medical science all have important learning value and practical application meaning.In view of specimen preprocessing in traditional mercury ion detecting method The shortcomings of reason is complicated, instrument and test value are expensive, analytical cycle is long, research emphasis is gradually transferred to mercury ion probe by people Research and development field.At present, there is higher anti-interference for the response type probe of mercury ion identification, but is stilled need using process By large-scale instrument, Glassless can be seldom realized.Liu Wei life et al. synthesis be by fluorogen, ethyleneoxy of naphthalimide The probe of recognition group can effective detection organic mercury, during recognition group of the ethyleneoxy as mercury ion, it is had mercury ion Preferable sensitivity and higher selectivity, but the detection of water body mercury ion can not be realized.In response type probe, chromene Nitrile fluorogen is based on own structural characteristics, is widely used in the field such as electroluminescent and chemical molecular sensing, but in mercury ion Detection field have no relevant report (M. E. Jun, B. Roy and K. H. Ahn, Chem. Commun., 2011, 47, 7583; J. Du, J. Fan, X. Peng, P. Sun, J. Wang, H. Li and S. Sun, Org.Lett., 2010, 12, 476;Song Xiangzhi;A kind of synthesis of fluorescence enhancement detection mercury ion probes of Liu Qian and its should With Chinese invention patents, CN103242195A, 2013-08-14; J. Jiang, W. Liu, J. Cheng, L. Yang, H. Jiang, D. Bai and W. Liu, Chem. Commun., 2012, 48, 8371)。
The content of the invention
The invention discloses a kind of synthetic method of the probe of the Visual retrieval mercury ion based on chromene nitrile, and root The detection of mercury ion is used it for the identification function of mercury ion according to it.
The mercury ion probe being related in the present invention, use 2- methyl chromene nitriles with 4- ethyleneoxies benzaldehyde for original Material, recognition group of the ethyleneoxy as mercury ion.
Technical scheme in the present invention is a kind of probe of the Visual retrieval mercury ion based on chromene nitrile, and it is closed It is as follows into route：
By 2- methyl chromene nitriles and 4- ethyleneoxies dissolution of benzaldehyde in ethanol or acetonitrile, added under room temperature condition The nafoxidine or piperidines of catalytic amount, yellow solid is separated out after being stirred at room temperature 3 hours, gained filter cake is pure probe after suction filtration Product.
The synthetic method and detection mode of the probe are described in detail by the embodiment of this specification.Visited in the present invention The application method of pin is：Probe is dissolved in ethanol or acetonitrile, after adding inorganic base, tested at room temperature.Add mercury ion Afterwards, ethyleneoxy is hydrolyzed to hydroxyl, hydroxyl and inorganic base reaction generation negative oxygen ion, and then causes fluorophor fluorescence to become Change, it is in aubergine to show as under the conditions of naked regard.Course of reaction is as follows：
The beneficial effects of the present invention are：（1）Synthesis condition is gentle, easy purification；（2）There is higher selection to mercury ion Property；（3）Detection process is simple and convenient, without large-scale instrument, testing result Glassless；（4）The probe is easy to preserve, and probe is solid Body is 0 under air exposureoC~50oC two weeks is unchanged, and probe solution room temperature preservation 30 days under air-proof condition is unchanged.
Brief description of the drawings
Fig. 1 is the color change before and after addition mercury ion under the conditions of the probe of the invention synthesized in ethanol sodium acid carbonate, Faint yellow and aubergine is followed successively by from left to right.
Fig. 2 be the probe that synthesizes of the present invention in ethanol, respectively in sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus bar Under part, Li+, Na+, Ca2+, Mg2+, Ba2+, Cu2+, Cd2+, Fe2+, Mn2+, Au3+, Fe3+, Al3+Mercury is added in the presence of mixed-cation Color change before and after ion, sodium carbonate and the color before and after addition mercury ion in the presence of mixed-cation are followed successively by from left to right Color change, sodium acid carbonate and mixed-cation in the presence of change, potassium carbonate and mixed-cation before and after addition mercury ion are deposited Color before and after adding mercury ion in the presence of the color change before and after lower addition mercury ion and saleratus and mixed-cation Change, is followed successively by faint yellow, aubergine, faint yellow, aubergine, faint yellow, aubergine, faint yellow, aubergine.
Fig. 3 be the probe that synthesizes of the present invention in acetonitrile, respectively in sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus bar Under part, Li+, Na+, Ca2+, Mg2+, Ba2+, Cu2+, Cd2+, Fe2+, Mn2+, Au3+, Fe3+, Al3+Mercury is added in the presence of mixed-cation Color change before and after ion, sodium carbonate and the color before and after addition mercury ion in the presence of mixed-cation are followed successively by from left to right Color change, sodium acid carbonate and mixed-cation in the presence of change, potassium carbonate and mixed-cation before and after addition mercury ion are deposited Color before and after adding mercury ion in the presence of the color change before and after lower addition mercury ion and saleratus and mixed-cation Change, is followed successively by faint yellow, aubergine, faint yellow, aubergine, faint yellow, aubergine, faint yellow, aubergine.
Fig. 4 is the proton nmr spectra for the probe that the present invention synthesizes.
Fig. 5 is the carbon-13 nmr spectra for the probe that the present invention synthesizes.
Fig. 6 is the probe and Hg that the present invention synthesizes2+The proton nmr spectra of hydrolysate after reaction.
Embodiment
Embodiment 1：Trans -2-（2-（4- ethyleneoxies）Styryl）The preparation of chromene -4- subunit malononitrile
By 2- methyl chromenes nitrile (104 mg, 0.5 mmoL) and 4- ethyleneoxies benzaldehyde (74 mg, 0.5 MmoL absolute ethyl alcohol (10 mL)) is dissolved in, 1 drop nafoxidine is added under room temperature condition, yellow is separated out after being stirred at room temperature 3 hours and is consolidated Body, by collected by suction filter cake, gained filter cake is product（Yield：124 mg；Yield：73.4%）.
1H NMR (400 MHz, DMSO) δ 8.74 (d, J = 8.4 Hz, 1H), 7.94 (t, J = 7.8 Hz, 1H), 7.86-7.68 (m, 4H), 7.62 (t, J = 7.7 Hz, 1H), 7.45 (d, J = 16.0 Hz, 1H), 7.17 (d, J = 8.5 Hz, 2H), 7.00 (dd, J = 13.5, 5.8 Hz, 2H), 4.86 (d, J = 13.4 Hz, 1H), 4.59 (d, J = 4.7 Hz, 1H).
13C NMR (100 MHz, DMSO) δ 158.79, 158.27, 153.43, 152.52, 147.87, 138.50, 135.90, 130.59, 130.35, 126.65, 125.14, 119.53, 118.85, 117.69, 117.60, 117.26, 116.35, 106.94, 97.01, 60.48。
Embodiment 2：The application of the probe of Visual retrieval mercury ion
The probe is dissolved in ethanol or acetonitrile, is configured to 1.0 × 10-5MoL/L probe solution, cationic aqueous solution are dense Degree is 3 × 10-3moL/L；3mL probe solutions are taken during test sample, add 1uL cationic solutions, alkalescence is tested after adding mercury ion Under the conditions of solution colour change；Fig. 1-Fig. 3 shows, in the presence of mercury ion, solution is changed into purplish red from yellow after adding inorganic base Color, visibility test can be realized to mercury ion；Fig. 2-Fig. 3 shows that probe has very high selectivity to mercury ion, and not By Li+, Na+, K+, Mg2+, Ba2+, Cu2+, Zn2+, Cd2+, Mn2+, Au3+, Fe3+, Al3+Deng the influence of metal ion.

Claims (2)

  1. A kind of 1. synthetic method of the probe of the Visual retrieval mercury ion based on chromene nitrile, it is characterised in that the probe Possess following structure：
    ,
    The synthetic method of the probe is：104 mg 2- methyl chromene nitriles and 74 mg 4- ethyleneoxy benzaldehydes are molten 1 drop nafoxidine is added under 10 mL absolute ethyl alcohols, room temperature condition, yellow solid is separated out after being stirred at room temperature 3 hours, by taking out Filter cake is collected in filter, and gained filter cake is probe product.
  2. 2. purposes of the probe in mercury ion is detected synthesized by method as claimed in claim 1, it is characterised in that its detection side Method is：The probe is dissolved in ethanol or acetonitrile, is configured to 1.0 × 10-5 MoL/L probe solution, after adding inorganic base, room Tested under temperature, wherein inorganic base is selected from sodium acid carbonate, sodium carbonate, saleratus, the aqueous solution or solid of potassium carbonate.
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CN106543097B (en) * 2016-09-22 2019-01-25 济南大学 It is a kind of using thiocarbonic acid phenyl ester as the highly selective mercury ion near infrared fluorescent probe of identification receptor
CN108558859B (en) * 2018-06-06 2021-08-24 湖北大学 Preparation and application of visible long-wave Hg2+ fluorescent probe based on benzopyran
CN109053711B (en) * 2018-09-21 2020-08-04 衡阳师范学院 Probe compound for mercury ion detection and preparation method and application thereof
CN112028810B (en) * 2019-07-23 2022-02-08 四川大学华西医院 Preparation method and application of mercury ion probe

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