CN104892533B - Tb (III) coordination compound and preparation method thereof and the application in detection cynocks - Google Patents
Tb (III) coordination compound and preparation method thereof and the application in detection cynocks Download PDFInfo
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- CN104892533B CN104892533B CN201510236442.0A CN201510236442A CN104892533B CN 104892533 B CN104892533 B CN 104892533B CN 201510236442 A CN201510236442 A CN 201510236442A CN 104892533 B CN104892533 B CN 104892533B
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- 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
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- 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
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Abstract
The invention discloses a kind of Tb (III) coordination compound and preparation method thereof and the application in detection cynocks.The structural formula of the coordination compound is that, with Isosorbide-5-Nitrae, 7 7-triazacyclononane derivants are part for which, and with Tb (III) cooperations, preparation method is extremely simple, and reaction condition is gentle.The features such as Tb (III) coordination compound of the present invention has fluorescence lifetime length, Stokes shift big and is coordinated unsaturated, can effectively be coordinated with neutral molecule cynocks, and Tb (III)5D4The T of energy level and cynocks1Energy level matched, it is ensured that effective energy transfer can occur therebetween and the fluorescence of Tb (III) coordination compound is significantly sensitized.Therefore, the coordination compound has stronger selectivity to cynocks, can realize the high selectivity to cynocks, high sensitivity sensing identification, and operating process is simple and convenient, and the efficient detection for cynocks provides a kind of new method of convenient, rapid low consumption.
Description
Technical field
The invention belongs to small molecule fluorescent field of sensing technologies, and in particular to Tb (III) complex fluorescent sensor Gao Xuan
Selecting property, highly sensitive detection organophosphorus pesticide cynocks.
Background technology
Pesticide be for prevent, eliminate or control to endanger agricultural, the disease of forestry, worm, grass and other harmful organisms and
Plant is adjusted purposefully, a class medicine of insect growth is referred to as.But the transition use of pesticide, abuse to ecological environment and the mankind
Health brings significant damage, and pollution by pesticides, pesticide intoxication event happen occasionally in recent years, it is seen that development is efficient, quick, convenient
The method of detection pesticide is most important for such event is prevented.At present, it is used for both at home and abroad detecting the handss of organophosphorus pesticide
Section mainly has gas chromatographic technique, high-efficient liquid phase chromatogram technology, immunoassay technology, enzymatic inhibition, biosensor technology
With fluorescence method etc..Wherein gas chromatograph instrument is heavy, expensive, and operation requires higher, strongly professional but also right
Sample carries out pretreatment, and cumbersome complexity is unfavorable for the flexible Application of Pesticides Testing and quick grasp.High performance liquid chromatography skill
Needed for art, the time of analysis is long, and sample is also required to carry out pretreatment, and process complexity is unfavorable for quick detection.Immunoassay is deposited
It is immunogenic prepare it is complicated, be difficult to obtain, the difficulty such as immunoreation has specificity, antibody selectivity is strong, and early stage throws
Enter greatly, be not suitable for China's national situation.The acetylcholine esterase used in enzymatic inhibition can not be preserved at normal temperatures, and the source of enzyme is not
Stable, the enzyme testing result of different batches is variant, and testing result is affected.Biosensor technique selectivity is not high, used
Enzyme is unstable, the deactivation phenomenom that there is enzyme.Fluorescent method has sensitivity high, and selectivity is good, fluorescence output signal abundant, operation
It is simple to wait remarkable advantage, it is expected to provide New Policy for the efficient detection of organophosphorus pesticide.
Cynocks are a kind of organophosphors broad spectrum pesticides, especially to the snout moth's larva of rice, rice plant skipper, planthopper, rice leaf roller,
The prevention effects such as leafhopper, mythimna separata are more notable.But cynocks can form phosphorylation acetyl gallbladder with acetylcholinesterase in human body
Alkali esterase, is suppressed acetylcholine esterase active, loses the ability for decomposing acetylcholine, causes acetylcholine in nerveous system
System aggregation, produces the dysfunction of corresponding nervous system.Therefore, high selectivity to cynocks, highly sensitive detection have emphatically
The meaning wanted.
The content of the invention
The technical problem to be solved is to overcome during traditional technique in measuring cynocks to sample pretreatment
Etc. troublesome operation and biological detecting method high cost, repeatability is poor the problems such as, there is provided it is a kind of to realize to cynocks
High selectivity, highly sensitive detection and fluorescence chemical sensor easy to operate, cheap --- Tb (III) coordination compound.
Solve the above problems employing technical scheme be the Tb (III) coordination compound structural formula it is as follows：
The preparation method of above-mentioned Tb (III) coordination compound is made up of following step：
1st, synthetic ligands
With ethanol as solvent, by Isosorbide-5-Nitrae, 7- 7-triazacyclononanes, triethylamine, acetbromamide are 1 in molar ratio:3～4:3～
4, reaction is refluxed, product is isolated and purified, the part shown in Formulas I is obtained.
2nd, synthesize Tb (III) coordination compound
Part shown in Formulas I is completely dissolved in distilled water, six chloride hydrate terbiums are added under stirring at normal temperature, continue stirring
24 hours, product is isolated and purified, obtain Tb (III) coordination compound, the wherein mol ratio of part and six chloride hydrate terbiums is 1:1～
1.5。
Purposes of Tb (III) coordination compounds of the present invention in detection cynocks, concrete grammar are as follows：
Tb (III) coordination compound is added Tb (III) complex solution that 50～60 μm of ol/L are prepared in methanol, Ran Houxiang
The cynocks standard sample of different volumes is wherein added, and the glimmering of the corresponding system of cynocks under variable concentrations is measured with fluorescence spectrophotometer
Light intensity simultaneously draws I/I0It is worth the standard curve with cynocks concentration change；Measure to be measured with fluorescence spectrophotometer according to the method described above
The fluorescence intensity of sample, according to the I/I of testing sample0Value, high selectivity identification by the linear equation of combined standard curve are killed
Snout moth's larva nitrile and in determining testing sample cynocks concentration.
Compared with prior art, the device have the advantages that as follows：
The preparation method of Tb (III) coordination compound of the present invention is extremely simple, and reaction condition is gentle, and prepared Tb (III) matches somebody with somebody
The features such as compound has fluorescence lifetime length, Stokes shift big and is coordinated unsaturated, can be effective with neutral molecule cynocks
Coordination, and Tb (III)5D4The T of energy level and cynocks1Energy level matched, it is ensured that effective energy can occur therebetween and turn
Move and be significantly sensitized the fluorescence of Tb (III) coordination compound.Therefore, the coordination compound has stronger selectivity, Neng Goushi to cynocks
High selectivity existing to cynocks, high sensitivity sensing identification, and operating process is simple and convenient, it is to avoid right in traditional method
The troublesome operations such as sample pretreatment and biological detecting method high cost, the problems such as repeatability is poor, are the efficient inspection of cynocks
Survey there is provided a kind of new method of convenient, rapid low consumption.
Description of the drawings
Fig. 1 is the fluorescence spectra of the fluorescence intensity with cynocks concentration change of Tb (III) coordination compound.
Fig. 2 is the linear diagram of the relative intensity of fluorescence with cynocks concentration change of Tb (III) coordination compound.
Fig. 3 is fluorescence intensity comparison diagram of Tb (III) coordination compounds in different organophosphorus pesticides.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1st, synthetic ligands
0.75g (5.6mmol) Isosorbide-5-Nitrae, 7- 7-triazacyclononanes are dissolved completely in 50mL ethanol, 2.8mL is added
(20.2mmol) triethylamine and 2.71g (19.6mmol) acetbromamide, after being heated to reflux stirring 6 hours, naturally cool to room temperature,
Sucking filtration, 35 DEG C of vacuum drying of gained white solid, obtains the part shown in Formulas I, and its reaction equation is as follows：
Gained part structural characterization data be：1H-NMR, δH(600MHz, D2O, Me4Si)：3.65 (6H,CH 2 CONH2),
2.96 (12H, NCH 2 CH 2 N).IR：(KBr, vMax/cm-1)：3507 (N-H), 1667 (C=O).1C-NMR, δC(600MHz, D2O,
Me4Si)：173.66 (3C, C=O), 56.91 (3C, CH2), 49.37 (12C, NCH 2 CH 2 N).MS (ESI, m/z)：Theoretical value：
301.1988([M+H]+), measured value：301.1992.
2nd, synthesize Tb (III) coordination compound
Part shown in 150.2mg (0.5mmol) Formulas I is dissolved completely in 40mL distilled water, is delayed under stirring at normal temperature
Slow Deca is dissolved completely in the six chloride hydrate terbium solution of 186.7mg (0.5mmol) of 30mL distilled water, stirring at normal temperature 24 hours,
Remove solvent under reduced pressure, gained solid matter is dissolved in 3mL methanol, and be added dropwise in the flask containing 100mL ether, have white heavy
Precipitation goes out, stirring at normal temperature sucking filtration after 1 hour, filter cake with after methanol dissolving by the above process with 100mL Diethyl ether recrystallizations three times, so
Afterwards with recrystallize with dichloromethane twice, the 35 DEG C of vacuum drying of gained solid matter, obtain Tb (III) coordination compound, its reactional equation
Formula is as follows：
Gained Tb (III) coordination compound structural characterization data be：IR (KBr, vMax/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+), actual measurement
Value：529.0546,247.0396.
Embodiment 2
Purposes of Tb (III) coordination compounds in detection cynocks, concrete grammar are as follows：
The methanol solution of 50 μm of ol/L Tb (III) coordination compounds is prepared, cynocks is added in the solution, make gained mixing
In solution, the concentration of cynocks is respectively 0,10,20,30,40,50,60,70,80,90,100,110,120,130,140,150 μ
Mol/L, then adopts FLS920 types single photon counting time resolution fluorescence spectral instrument in maximum excitation wavelength for 275nm, transmitting
Wavelength is that fluorescence intensity (exciting slit is 2nm, and transmite slit is 3nm) is measured at 547nm, and fluorescence intensity becomes with cynocks concentration
The fluorescence spectra of change is shown in Fig. 1, and draws I/I0It is worth the linear diagram with cynocks concentration change, as a result sees Fig. 2.
As seen from Figure 1, the fluorescence intensity of Tb (III) coordination compound with system cynocks concentration increase change it is very bright
It is aobvious, 55 times or so can be sensitized, illustrate that Tb (III) coordination compounds are very high to the detection sensitivity of cynocks；When the concentration of cynocks it is big
When 100 μm of ol/L, fluorescence intensity is not further added by.From Figure 2 it can be seen that cynocks are when concentration is 0～100 μm of ol/L, I/I0Value
Linear with cynocks concentration, linear equation is：
Y=1.78033+0.53408x
In formula, y is I/I0Value, x are cynocks concentration, and correlation coefficient r is 0.99768, from correlation coefficient, I/I0Value with
The linear relationship of cynocks concentration is fine.
In order to prove beneficial effects of the present invention, inventor is distinguished to the methanol solution of 50 μm of ol/L Tb (III) coordination compounds
Add concentration be 100 μm of ol/L cynocks (2), Profenofos (3), chlopyrifos (4), Rogor (5), diazinon (6), phoxim (7),
Fenthion (8), parathion-methyl (9), the methanol solution of dichlorvos (10), and with 275nm as excitation wavelength, which is recorded in maximum
Launch wavelength is the fluorescence intensity at 547nm, while the methanol solution of Tb (III) coordination compound not add any organophosphorus pesticide
As blank (1), Fig. 3 is as a result seen.
As seen from Figure 3, in this 9 kinds of organophosphorus pesticides, only cynocks have bright to the fluorescence of TbL (III) coordination compound
Aobvious sensitization effect, and other organophosphorus pesticides are not produced to its fluorescence intensity and are significantly affected, and illustrate that Tb of the present invention (III) coordinates
Thing has very high selectivity to cynocks.By calculating, its detection limit to cynocks can reach 59nmol/L.
Claims (4)
1. a kind of Tb (III) coordination compound, it is characterised in that the structural formula of the coordination compound is as follows：
2. the preparation method of Tb (III) coordination compound described in a kind of claim 1, it is characterised in that it is synthesized by following step：
(1) synthetic ligands
With ethanol as solvent, by Isosorbide-5-Nitrae, 7- 7-triazacyclononanes, triethylamine, acetbromamide are 1 in molar ratio:3～4:3～4, return
Stream stirring reaction, isolates and purifies product, obtains the part shown in Formulas I；
(2) synthesize Tb (III) coordination compound
Part shown in Formulas I is completely dissolved in distilled water, six chloride hydrate terbiums are added under stirring at normal temperature, continue stirring 24 little
When, product is isolated and purified, Tb (III) coordination compound is obtained, the wherein mol ratio of part and six chloride hydrate terbiums is 1:1～1.5.
3. purposes of Tb (III) coordination compounds described in claim 1 in detection cynocks.
4. Tb (III) coordination compounds according to claim 3 detection cynocks in purposes, it is characterised in that：By Tb
(III) Tb (III) complex solution of 50～60 μm of ol/L during coordination compound adds methanol, is prepared, different volumes are added thereto to
Cynocks standard sample, with fluorescence spectrophotometer measure variable concentrations under cynocks correspondence system fluorescence intensity and draw I/I0
It is worth the standard curve with cynocks concentration change；Measure the fluorescence intensity of testing sample according to the method described above with fluorescence spectrophotometer,
According to the I/I of testing sample0Value, by the linear equation of combined standard curve, high selectivity recognizes cynocks and test sample is treated in determination
The concentration of cynocks in product.
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| CN105384789B (en) * | 2015-10-16 | 2018-01-12 | 陕西师范大学 | Amphipathic guanosine derivative and preparation method thereof and the application in cytidine sensing identification |
| 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 |
Citations (3)
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| CN1189105A (en) * | 1995-06-26 | 1998-07-29 | 康凯有限公司 | Compounds with chelation affinity and selectivity for first transition series elements, and their use in medical therapy and diagenosis |
| WO2012155076A2 (en) * | 2011-05-11 | 2012-11-15 | The Research Foundation Of State University Of New York | Imaging contrast agents and uses thereof |
| WO2015038943A1 (en) * | 2013-09-12 | 2015-03-19 | The Research Foundation For The State University Of New York University At Buffalo | Macrocycles, cobalt and iron complexes of same, and methods of making and using same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189105A (en) * | 1995-06-26 | 1998-07-29 | 康凯有限公司 | Compounds with chelation affinity and selectivity for first transition series elements, and their use in medical therapy and diagenosis |
| WO2012155076A2 (en) * | 2011-05-11 | 2012-11-15 | The Research Foundation Of State University Of New York | Imaging contrast agents and uses thereof |
| WO2015038943A1 (en) * | 2013-09-12 | 2015-03-19 | The Research Foundation For The State University Of New York University At Buffalo | Macrocycles, cobalt and iron complexes of same, and methods of making and using same |
Non-Patent Citations (2)
| Title |
|---|
| Nitrogen versus oxygen co-ordination of carboxamidefunctionalized triazacyclononane ligands in transition metal ion complexes;Thomas Weyhermüller，等;《J. Chem. Soc., Dalton Trans》;19980101;第22卷;第3805-3814页 * |
| Synthesis of N-substituted cyclic triglycines and their response to metal ions;Hideaki Hioki，等;《Tetrahedron Letters》;20041231;第45卷;第1091–1094页 * |
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