CN105203606B - A kind of preparation method and applications based on copper metal organic frame complex modified gold electrode - Google Patents
A kind of preparation method and applications based on copper metal organic frame complex modified gold electrode Download PDFInfo
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- CN105203606B CN105203606B CN201510707322.4A CN201510707322A CN105203606B CN 105203606 B CN105203606 B CN 105203606B CN 201510707322 A CN201510707322 A CN 201510707322A CN 105203606 B CN105203606 B CN 105203606B
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Abstract
The present invention discloses a kind of preparation method and applications based on copper metal organic frame complex modified gold electrode, is prepared using hydro-thermal method, steps are as follows: 1) preparing cupric coordination compound { [CuL (H2O)] 0.5DMA }；2) preparation of { [CuL (H2O)] 0.5DMA } metallic organic frame complex modified electrode；3) modified electrode for detecting l-methionine and D-Met respectively.The invention has the advantages that the present invention is prepared for metallic organic frame complex { [CuL (H2O)] 0.5DMA } for the first time, and structural characterization is carried out to it, it is prepared for { [CuL (H2O)] 0.5DMA } modification novel electrochemical sensor, the detection applied to l-methionine and D-Met chiral isomer.Modified electrode preparation is simple, cheap, has significant technical effect.
Description
Technical field
The present invention relates to a kind of preparation method based on copper metal organic frame complex and repairing based on this substance
Adorn electrode preparation method and its D-Met and l-methionine chiral isomer detection technique.
Background technique
Methionine, also known as methionine are a kind of sulfur-bearing essential amino acids.Various Containing Sulfurs in methionine and organism
The metabolism for closing object is closely related, and organism must convert in vivo D type to L-type and could be utilized by body.Feed, food,
Medicine, the multiple fields such as agricultural and environmental monitoring are widely used, and how efficiently and accurately realizes that methionine chirality is different
The detection identification of structure body is the urgent problem to be solved faced now.
In recent years, metal-organic framework (MOF) is with its unique porous structure, the coordination mode of multiplicity, Yi Jiqi
Application in fields such as the energy, electrochemistry, catalysis, absorption, energy storage obtains region of chemistry and widely pays close attention to.In electrochemical field, grind
The person's of studying carefully discovery is by that can carry out Electrochemical Detection to many kinds of substance in electrode face finish MOF material, such as Diana M et al. benefit
Use Pmo12V2@MIL-101 (Cr) porous modified electrode realizes the synchronous detection of dopamine and ascorbic acid；Hadi
Hosseini etc. has researched and developed Au-SH-SiO2@Cu-MOF electrochemical sensor is simultaneously applied to half Guang of electrocatalytic oxidation L-
Propylhomoserin obtains good effect.Therefore, MOF material has potential application prospect in electrochemical field.Studies have found that only
There are a small number of MOF materials that there is electronics conduction function, this has just limited to MOF material in the promotion and application of electrochemical field.
Summary of the invention
Goal of the invention of the invention is to provide the novel metal organic frame of one kind in order to solve above-mentioned problem and match
The preparation method for closing object, prepares novel electrochemical sensor using this metal framework complex, and be applied to D- first sulphur
The electrochemical recognition of propylhomoserin and l-methionine.
Technical solution of the present invention:
A kind of preparation method based on copper metal organic frame complex modified gold electrode, is prepared, step using hydro-thermal method
It is as follows:
1) metallic organic frame complex Cu-MOF { [CuL (H2O)] 0.5DMA } synthesis:
0.2mmol Copper dichloride dihydrate is dissolved in 2mL distilled water and is prepared into stock solution A, by 0.2mmol thiophene -2,5-
Dicarboxylic acids (H2L it) is added in 2mL n,N-dimethylacetamide and is prepared into stock solution B, then mix stock solution A and stock solution B
It closes, is placed in 90 DEG C of baking oven and reacts 48 hours, filtered after Temperature fall, obtained solid is washed with distilled water 2-6 times, is obtained
To blue crystalline solid metallic organic frame complex；
2){[CuL(H2O)] 0.5DMA } complex decorating electrode preparation:
0.25g chitosan is weighed, is dissolved in the aqueous acetic acid of 100mL1%, limpid homogeneous and transparent stock solution C is obtained,
Weigh 0.020g { [CuL (H2O)] 0.5DMA } complex, it is added in above-mentioned C under ultrasound condition, obtains jade-green suspended
Liquid takes the 10 μ L suspension point in clean glassy carbon electrode surface, and 12 hours naturally dries obtain { [CuL (H2O)]·
0.5DMA } modified electrode.
The present invention also provides a kind of applications based on copper metal organic frame complex modified gold electrode, i.e., it is in D- first
The detection technique of methyllanthionine and l-methionine chiral isomer:
Detect D-Met and l-methionine:
With { [CuL (H2O)] 0.5DMA } modified electrode as working electrode, saturated calomel electrode as reference electrode,
Platinum electrode forms three-electrode system as auxiliary electrode, electrochemical workstation is accessed, at phosphate buffer solution (pH=6.8)
D-Met and l-methionine are detected respectively.
The phosphate buffer solution is by sodium dihydrogen phosphate (0.2mol/L) aqueous solution and disodium hydrogen phosphate aqueous solution
(0.2mol/L) is mixed with.PH value is determined by pH acidometer.
The invention has the advantages that the present invention is prepared for metallic organic frame complex { [CuL (H for the first time2O)]·
0.5DMA }, structural characterization has been carried out to it, has been prepared for { [CuL (H2O)] 0.5DMA } modification novel electrochemical sensor, it answers
It is simple for the preparation of the detection of the D-Met and l-methionine modified electrode, it is cheap, there is significant technology effect
Fruit.
Detailed description of the invention
Fig. 1 is the { [CuL (H2O)] 0.5DMA } Advances in crystal X-ray diffraction parsing gained molecular structure.
Fig. 2 is the { [CuL (H2O)] 0.5DMA } powder x-ray diffraction figure and monocrystalline analogue data comparison diagram.
Fig. 3 is the { [CuL (H2O)] 0.5DMA } modified electrode detection D-Met.
Fig. 4 is the { [CuL (H2O)] 0.5DMA } modified electrode detection l-methionine.
Specific embodiment
The present invention is based on the preparation methods of copper metal organic frame complex modified gold electrode, are prepared using hydro-thermal method, step
It is rapid as follows:
1) metallic organic frame complex { [CuL (H2O)] 0.5DMA } synthesis
Weigh 0.0341g CuCl2·2H2O is dissolved in 2mL distilled water, is prepared into stock solution A, weighs 0.0344g thiophene-
2,5- dicarboxylic acids, which are added in 2mL n,N-dimethylacetamide, is prepared into stock solution B, then mixes stock solution A and stock solution B
It closes, is placed in closed container, is placed in 90 DEG C of baking oven and reacts 48 hours, cool down 48 hours, the solid being obtained by filtration, with steaming
Distilled water is washed 2-6 times, and it is metallic organic frame complex { [CuL (H that it is crystalline, which to obtain light green color,2O)]·0.5DMA}；
Metallic organic frame complex { [CuL (the H2O)] 0.5DMA } property representation:
(1) single crystal structure determination
Crystal structure crystal structure determination uses Supernova type X-ray single crystal diffractometer, using by graphite monochromatic
The Mo K alpha ray of changeFor Incident Irradiation Source, withScanning mode collects point diffraction, by minimum two
Multiplication is corrected to obtain cell parameter, solves crystal structure from difference Fourier electron-density map using SHELXL-97 direct method,
And it is corrected through Lorentz and polarity effect.All H atoms are synthesized by difference Fourier and are calculated through ideal position and determine.It is brilliant
Body determination data is shown in Table 1
The crystallographic data of 1 compound of table
Fig. 1 is the compound { [CuL (H2O)] 0.5DMA } single crystal diffraction parsing gained minimum structural unit figure,
Contain a copper ion, a dehydrogenation ligand L in the compound molecule as seen from the figure-, a water of coordination and free solvent molecule
DMA.The occupation rate of Cu1 and Cu2 is respectively 0.5.
(2) powder x-ray diffraction measures:
Powder x-ray diffraction data is 40kV in collecting completion, operation voltage on Rigaku D/Max-2500 diffractometer,
Electric current is 100mA, and being used in test through graphite monochromatised copper target X-ray is Incident Irradiation Source.Density data, which is collected, uses 2
θ/θ scan pattern, in carrying out continuous scanning within the scope of 3 ° to 60 °, scanning speed is 8 °s/sec, and span is 0.02 °/time.Test number
Cerius2 program is used according to fitting, the conversion of mono-crystalline structures powder x-ray diffraction spectrum analog uses software Mercury 1.42.
Fig. 2 is the { [CuL (H2O)] 0.5DMA } complex powder x-ray diffraction figure with according to single crystal data mould
Quasi- comparison diagram.
2){[CuL(H2O)] 0.5DMA } complex decorating electrode preparation:
0.25g chitosan is weighed, is dissolved in the aqueous acetic acid of 100mL1%, limpid homogeneous and transparent stock solution C is obtained.
Weigh 0.020g { [CuL (H2O)] 0.5DMA } complex, it is added in above-mentioned C under ultrasound condition, obtains jade-green suspended
Liquid.Take the 10 μ L suspension point in clean glassy carbon electrode surface, 12 hours naturally dries obtain { [CuL (H2O)]·0.5DMA}
Modified electrode.
Gained { [CuL (H2O)] 0.5DMA } complex decorating gold electrode of the invention, can be used for l-methionine and D- first
The detection of methyllanthionine, detection method are as follows:
(1){[CuL(H2O)] 0.5DMA } detection of the complex decorating electrode to l-methionine:
By metallic organic frame complex obtained { [CuL (H2O)] 0.5DMA } modified electrode as working electrode, satisfies
With calomel electrode as reference electrode, platinum electrode forms three-electrode system as auxiliary electrode, accesses electrochemical workstation,
L-methionine is detected in phosphate buffer solution (pH=6.8).The modified electrode has good sound to l-methionine
It answers, sees Fig. 3.
(2){[CuL(H2O)] 0.5DMA } detection of the complex decorating electrode to D-Met:
By metallic organic frame complex obtained { [CuL (H2O)] 0.5DMA } modified electrode as working electrode, satisfies
With calomel electrode as reference electrode, platinum electrode forms three-electrode system as auxiliary electrode, accesses electrochemical workstation,
D-Met is detected in phosphate buffer solution (pH=6.8).The modified electrode has good sound to D-Met
It answers, sees Fig. 4.
Claims (2)
1. a kind of application based on copper metal organic frame complex modified electrode, it is characterised in that: for molten in phosphoric acid buffer
In liquid, completion detects D-Met or l-methionine,
It is as follows to the detecting step of l-methionine:
By metallic organic frame complex obtained { [CuL (H2O)] 0.5DMA } for modified electrode as working electrode, saturation is sweet
Mercury electrode forms three-electrode system as auxiliary electrode, electrochemical workstation is accessed, in phosphorus as reference electrode, platinum electrode
Acid buffering solution detects l-methionine；
It is as follows to the detecting step of D-Met:
By metallic organic frame complex obtained { [CuL (H2O)] 0.5DMA } for modified electrode as working electrode, saturation is sweet
Mercury electrode forms three-electrode system as auxiliary electrode, electrochemical workstation is accessed, in phosphorus as reference electrode, platinum electrode
Acid buffering solution detects D-Met；
Wherein metallic organic frame complex { [CuL (H2O)] 0.5DMA } modified electrode is prepared by the following preparation method, it walks
It is rapid as follows:
1) metallic organic frame complex { [CuL (H2O)] 0.5DMA } synthesis:
Copper dichloride dihydrate is dissolved in distilled water and is prepared into stock solution A, 2,5-ThiophenedicarboxyliAcid Acid is added to N, N- dimethyl
It is prepared into stock solution B in acetamide, then mixes stock solution A with stock solution B, is placed in 90 DEG C of baking oven and reacts 48 hours,
It is filtered after Temperature fall, obtained solid is washed with distilled water 2-6 times, obtain blue crystalline solid metal organic frame cooperation
Object；
2){[CuL(H2O)] 0.5DMA } complex decorating electrode preparation:
0.25g chitosan is weighed, is dissolved in the aqueous acetic acid of 100mL1%, limpid homogeneous and transparent stock solution C is obtained, weighs
0.020g{[CuL(H2O)] 0.5DMA } complex, it is added in above-mentioned C under ultrasound condition, obtains jade-green suspension, take
For the 10 μ L suspension point in clean glassy carbon electrode surface, 12 hours naturally dries obtain { [CuL (H2O)] 0.5DMA } it repairs
Adorn electrode；
Copper chloride dihydrate described in step 1), thiophene -2,5- dicarboxylic acids molar ratio be 1:1；Distilled water and N, N- dimethyl second
The volume ratio of amide is 1:1；The Copper dichloride dihydrate is 0.2mmol, and the distilled water is 2mL, thiophene -2,5- dicarboxyl
Acid is 0.2mmol, and the n,N-dimethylacetamide is 2mL.
2. the application according to claim 1 based on copper metal organic frame complex modified electrode, it is characterised in that: phosphorus
Acid buffering pH value of solution=6.8.
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| CN105977467A (en) * | 2016-07-01 | 2016-09-28 | 北京工业大学 | Preparation method for preparing Co3O4@CoP composite electrode based on MOF template |
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| CN108444500A (en) * | 2018-03-12 | 2018-08-24 | 天津大学 | Flexible sensing device based on metal-organic framework material and preparation method thereof |
| CN108562627B (en) * | 2018-04-09 | 2019-11-26 | 江南大学 | A kind of electrochemical sensor based on chiral covalent organic framework compound |
| CN110095520B (en) * | 2019-05-08 | 2021-10-12 | 哈尔滨理工大学 | Working electrode for electrochemical sensor based on Cs/Ce-MOF |
| CN112649413B (en) * | 2020-11-03 | 2022-03-25 | 中山大学 | Nano-gold-MOF composite flexible SERS film substrate and preparation method and application thereof |
| CN116516433B (en) * | 2022-01-24 | 2024-04-26 | 中国科学院深圳先进技术研究院 | Green rapid preparation method of metal organic framework compound film coating |
| CN115805062B (en) * | 2022-11-29 | 2024-04-26 | 四川轻化工大学 | Double-ligand Met-MIL-101 physical adsorbent and preparation method and application thereof |
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