CN104892533A - Tb(III) complex, preparation method therefor and application in detecting cyanophos - Google Patents

Tb(III) complex, preparation method therefor and application in detecting cyanophos Download PDF

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Publication number
CN104892533A
CN104892533A CN201510236442.0A CN201510236442A CN104892533A CN 104892533 A CN104892533 A CN 104892533A CN 201510236442 A CN201510236442 A CN 201510236442A CN 104892533 A CN104892533 A CN 104892533A
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China
Prior art keywords
iii
cynock
title complex
complex
cyanophos
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CN201510236442.0A
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CN104892533B (en
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刘静
全静苗
雷海瑞
严军林
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Shaanxi Normal University
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Shaanxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D255/00—Heterocyclic compounds containing rings having three nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D249/00 - C07D253/00
    • C07D255/02—Heterocyclic compounds containing rings having three nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D249/00 - C07D253/00 not condensed with other rings
    • 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
    • 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
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms

Abstract

The invention discloses Tb(III) complex, a preparation method therefor and an application in detecting cyanophos. A structural formula of the complex is as shown in the specification. The complex is formed by taking a 1,4,7-triazacyclononane derivative as a ligand to coordinate with Tb (III); and the preparation method is extremely simple, and gentle in reaction condition. The Tb(III) complex disclosed by the invention has the characteristics such as long fluorescent lifetime, large Stokes shift, coordinative unsaturation and the like, and can be effectively coordinated with a neutral molecule cyanophos; and moreover, the 5D4 energy level of the Tb (III) is highly matched with the T1 energy level of the cyanophos, so that effective energy transfer is ensured to generate between the Tb (III) and the cyanophos, and the fluorescence of the Tb (III) is greatly sensitized. Therefore, the complex has relatively strong selectivity on the cyanophos and can realize high-selectivity and high-sensitivity sensing and recognition of the cyanophos; and moreover, the operation process is simple and convenient, and a convenient, quick and low-consumption novel method is provided for efficiently detecting the cyanophos.

Description

Tb (III) title complex and preparation method thereof and the application in detection cynock
Technical field
The invention belongs to small molecule fluorescent field of sensing technologies, be specifically related to Tb (III) complex fluorescent sensor highly selective, highly sensitive detection organophosphorus pesticide cynock.
Background technology
Agricultural chemicals is the class medicine general designation for preventing, eliminating or control to endanger agricultural, the disease of forestry, worm, grass and other harmful organisms and on purpose regulating plant, insect growth.But the transition of agricultural chemicals uses, abuses and bring significant damage to ecotope and human health, and pesticidal contamination, pesticide intoxication event happen occasionally in recent years, visible development is efficient, fast, the method for easy detection agricultural chemicals is most important for stopping this type of event.At present, the means both at home and abroad for detecting organophosphorus pesticide mainly contain gas chromatographic technique, high-efficient liquid phase chromatogram technology, immunoassay technology, enzymatic inhibition, biosensor technology and fluorescent method etc.Wherein gas chromatograph instrument is heavy, and expensive, operational requirement is higher, strongly professional, but also will carry out pre-treatment to sample, and complex operation is complicated, is unfavorable for the flexible Application of Pesticides Testing and grasps fast.The high-efficient liquid phase chromatogram technology required time analyzed is long, and also need to carry out pre-treatment to sample, process complexity is unfavorable for rapid detection.Immunoassay exist immunogenic preparation complicated, be difficult to obtain, the difficulty such as immune response has specificity, antibody selectivity is strong, and early investment is large, is not suitable for China's national situation.The Pseudocholinesterase used in enzymatic inhibition can not be preserved at normal temperatures, and the source of enzyme is unstable, and the enzyme detected result of different batches is variant, and detected result is affected.Biosensor technique selectivity is not high, and enzyme used is unstable, there is the deactivation phenomenom of enzyme.The remarkable advantages such as fluorescent method has highly sensitive, and selectivity is good, fluorescence output signal is abundant, simple to operate, the efficient detection be expected to for organophosphorus pesticide provides New Policy.
Cynock is a kind of organophosphorus broad spectrum pesticide, more remarkable to prevention effect such as the snout moth's larva of rice, rice plant skipper, planthopper, rice leaf roller, leafhopper, mythimna separatas especially.But cynock can form phosphorylation acetylcholinesterase with acetylcholinesterase in human body, acetylcholine esterase active is suppressed, lose the ability of decomposing vagusstoff, cause vagusstoff to be assembled in neural system, produce corresponding neural dysfunction.Therefore, the highly selective of cynock, highly sensitive detection are had great significance.
Summary of the invention
Technical problem to be solved by this invention to be to overcome in traditional technique in measuring cynock process the troublesome operation such as sample pretreatment and the problem such as biological detecting method cost is high, circulation ratio is poor, provides a kind of and can realize the highly selective to cynock, highly sensitive detection and easy and simple to handle, cheap fluorescence chemical sensor---Tb (III) title complex.
The technical scheme adopted that solves the problem is that the structural formula of this Tb (III) title complex is as follows:
The preparation method of above-mentioned Tb (III) title complex is made up of following step:
1, synthetic ligands
Be solvent with ethanol, by Isosorbide-5-Nitrae, 7-7-triazacyclononane, triethylamine, bromoacetamide are 1:3 ~ 4:3 ~ 4 in molar ratio, and return stirring reacts, and separation and purification product, obtains the part shown in formula I.
2, Tb (III) title complex is synthesized
Be dissolved in completely in distilled water by part shown in formula I, add six chloride hydrate terbiums under stirring at normal temperature, continue stirring 24 hours, separation and purification product, obtains Tb (III) title complex, and wherein the mol ratio of part and six chloride hydrate terbiums is 1:1 ~ 1.5.
Tb of the present invention (III) title complex is detecting the purposes in cynock, and concrete grammar is as follows:
Tb (III) title complex is added in methyl alcohol, Tb (III) complex solution of preparation 50 ~ 60 μm of ol/L, then add the cynock standard model of different volumes wherein, measure the fluorescence intensity of the corresponding system of cynock under different concns by fluorescence spectrophotometer and draw I/I 0be worth the typical curve with cynock change in concentration; The fluorescence intensity of testing sample is measured according to the method described above, according to the I/I of testing sample by fluorescence spectrophotometer 0value, the linear equation of combined standard curve gets final product highly selective identification cynock and determines the concentration of cynock in testing sample.
Compared with prior art, the beneficial effect that has of the present invention is as follows:
The preparation method of Tb of the present invention (III) title complex is extremely simple, reaction conditions is gentle, prepared Tb (III) title complex has that fluorescence lifetime is long, Stokes shift is large and the feature such as coordination is unsaturated, can coordination effective in neutral molecule cynock, and Tb (III) 5d 4the T of energy level and cynock 1energy level matched, guarantees can to occur the fluorescence of useful energy transfer and significantly sensitization Tb (III) title complex therebetween.Therefore, this title complex has stronger selectivity to cynock, the highly selective to cynock, the identification of highly sensitive sensing can be realized, and operating process is simple and convenient, avoid in traditional method to the troublesome operation such as sample pretreatment and biological detecting method cost high, the problems such as circulation ratio is poor, the efficient detection for cynock provides a kind of novel method of convenient, rapid low consumption.
Accompanying drawing explanation
Fig. 1 is the fluorescence spectrum figure of fluorescence intensity with cynock change in concentration of Tb (III) title complex.
Fig. 2 is the linear diagram of relative intensity of fluorescence with cynock change in concentration of Tb (III) title complex.
Fig. 3 is the fluorescence intensity comparison diagram of Tb (III) title complex in different organophosphorus pesticide.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in more detail, but protection scope of the present invention is not limited only to these embodiments.
Embodiment 1
1, synthetic ligands
By 0.75g (5.6mmol) 1,4,7-7-triazacyclononane is dissolved in 50mL ethanol completely, add 2.8mL (20.2mmol) triethylamine and 2.71g (19.6mmol) bromoacetamide again, reflux naturally cools to room temperature after stirring 6 hours, suction filtration, the 35 DEG C of vacuum-dryings of gained white solid, obtain the part shown in formula I, its reaction equation is as follows:
The structural characterization data of gained part are: 1h-NMR, δ h(600MHz, D 2o, Me 4si): 3.65 (6H, cH 2 cONH 2), 2.96 (12H, N cH 2 cH 2 n).IR：(KBr，v Max/cm -1)：3507(N-H)，1667(C＝O)。 1C-NMR，δ C(600MHz，D 2O，Me 4Si)：173.66(3C，C＝O)，56.91(3C，CH 2)，49.37(12C，N CH 2 CH 2 N)。MS (ESI, m/z): theoretical value: 301.1988 ([M+H] +), measured value: 301.1992.
2, Tb (III) title complex is synthesized
Part shown in 150.2mg (0.5mmol) formula I is dissolved in 40mL distilled water completely, CL is slowly dripped in 186.7mg (0.5mmol) the six chloride hydrate terbium solution of 30mL distilled water under stirring at normal temperature, stirring at normal temperature 24 hours, remove solvent under reduced pressure, gained solid matter is dissolved in 3mL methyl alcohol, and be dropwise added in the flask containing 100mL ether, adularescent Precipitation, stirring at normal temperature is suction filtration after 1 hour, above method 100mL Diethyl ether recrystallization is pressed three times after filter cake dissolve with methanol, then twice, methylene dichloride recrystallization is used, the 35 DEG C of vacuum-dryings of gained solid matter, obtain Tb (III) title complex, its reaction equation is as follows:
The structural characterization data of gained Tb (III) title complex are: IR (KBr, v max/ cm -1): 3370,3117 (N-H), 1661,1593 (C=O).MS (ESI, m/z): theoretical value: 529.0541 ([M-Cl] +), 247.0426 ([M-2Cl] 2+), measured value: 529.0546,247.0396.
Embodiment 2
Tb (III) title complex is detecting the purposes in cynock, and concrete grammar is as follows:
Prepare the methanol solution of 50 μm of ol/L Tb (III) title complexs, cynock is added in this solution, the concentration of cynock in gained mixing solutions is made to be respectively 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150 μm of ol/L, then FLS920 type single photon counting time resolution fluorescence spectral instrument is adopted to be 275nm at maximum excitation wavelength, emission wavelength is that 547nm place measurement fluorescence intensity (excites slit to be 2nm, transmitting slit is 3nm), fluorescence intensity is shown in Fig. 1 with the fluorescence spectrum figure of cynock change in concentration, and draw I/I 0be worth the linear diagram with cynock change in concentration, the results are shown in Figure 2.
As seen from Figure 1, the fluorescence intensity of Tb (III) title complex along with cynock concentration in system increase change clearly, can sensitization about 55 times, illustrate that Tb (III) title complex is very high to the detection sensitivity of cynock; When the concentration of cynock is greater than 100 μm of ol/L, fluorescence intensity no longer increases.As seen from Figure 2, cynock when concentration is 0 ~ 100 μm of ol/L, I/I 0value is linear with cynock concentration, and linear equation is:
y＝1.78033+0.53408x
In formula, y is I/I 0value, x is cynock concentration, and correlation coefficient r is 0.99768, from relation conefficient, I/I 0value is fine with the linear relationship of cynock concentration.
In order to prove beneficial effect of the present invention, it is 100 μm of ol/L cynocks (2) that contriver adds concentration respectively to the methanol solution of 50 μm of ol/L Tb (III) title complexs, Profenofos (3), Chlorpyrifos 94 (4), Rogor (5), diazinon (6), Volaton (7), Tiguvon (8), parathion-methyl (9), the methanol solution of SD-1750 (10), and be excitation wavelength with 275nm, record the fluorescence intensity that it is 547nm place at maximum emission wavelength, simultaneously not add the methanol solution of Tb (III) title complex of any organophosphorus pesticide as blank (1), the results are shown in Figure 3.
As seen from Figure 3, in these 9 kinds of organophosphorus pesticides, the fluorescence of cynock to TbL (III) title complex is only had to have obvious sensitization effect, and other organophosphorus pesticides do not produce obvious impact to its fluorescence intensity, illustrate that Tb of the present invention (III) title complex has very high selectivity to cynock.Known by calculating, it can reach 59nmol/L to the detection limit of cynock.

Claims (4)

1. Tb (III) title complex, is characterized in that the structural formula of this title complex is as follows:
2. a preparation method for Tb according to claim 1 (III) title complex, is characterized in that it is synthesized by following step:
(1) synthetic ligands
Be solvent with ethanol, by Isosorbide-5-Nitrae, 7-7-triazacyclononane, triethylamine, bromoacetamide are 1:3 ~ 4:3 ~ 4 in molar ratio, and return stirring reacts, and separation and purification product, obtains the part shown in formula I;
(2) Tb (III) title complex is synthesized
Be dissolved in completely in distilled water by part shown in formula I, add six chloride hydrate terbiums under stirring at normal temperature, continue stirring 24 hours, separation and purification product, obtains Tb (III) title complex, and wherein the mol ratio of part and six chloride hydrate terbiums is 1:1 ~ 1.5.
3. Tb according to claim 1 (III) title complex is detecting the purposes in cynock.
4. Tb according to claim 3 (III) title complex is detecting the purposes in cynock, it is characterized in that: Tb (III) title complex is added in methyl alcohol, Tb (III) complex solution of preparation 50 ~ 60 μm of ol/L, add the cynock standard model of different volumes wherein, measure the fluorescence intensity of the corresponding system of cynock under different concns by fluorescence spectrophotometer and draw I/I 0be worth the typical curve with cynock change in concentration; The fluorescence intensity of testing sample is measured according to the method described above, according to the I/I of testing sample by fluorescence spectrophotometer 0value, the linear equation of combined standard curve gets final product highly selective identification cynock and determines the concentration of cynock in testing sample.
CN201510236442.0A 2015-05-11 2015-05-11 Tb (III) coordination compound and preparation method thereof and the application in detection cynocks Expired - Fee Related CN104892533B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105384789A (en) * 2015-10-16 2016-03-09 陕西师范大学 Amphiphilicity guanosine derivative, and preparation method therefor and application thereof in cytidine triphosphate sensing and recognition
CN106092983A (en) * 2016-06-02 2016-11-09 合肥学院 A kind of Y detecting organochlorine pesticide2o3: Tb3+@SiO2nH2fluorescent sensor array preparation method

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105384789A (en) * 2015-10-16 2016-03-09 陕西师范大学 Amphiphilicity guanosine derivative, and preparation method therefor and application thereof in cytidine triphosphate sensing and recognition
CN106092983A (en) * 2016-06-02 2016-11-09 合肥学院 A kind of Y detecting organochlorine pesticide2o3: Tb3+@SiO2nH2fluorescent sensor array preparation method
CN106092983B (en) * 2016-06-02 2018-10-12 合肥学院 A kind of Y of detection organo-chlorine pesticide2O3:Tb3+@SiO2-NH2Fluorescent sensor array preparation method

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