CN108299474B - One-dimensional Zn functional complex and preparation method and application thereof - Google Patents

One-dimensional Zn functional complex and preparation method and application thereof Download PDF

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CN108299474B
CN108299474B CN201810027855.1A CN201810027855A CN108299474B CN 108299474 B CN108299474 B CN 108299474B CN 201810027855 A CN201810027855 A CN 201810027855A CN 108299474 B CN108299474 B CN 108299474B
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吴晓琴
魏学红
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Shanxi University
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Abstract

The invention provides a one-dimensional Zn functional complex and a preparation method and application thereof. The molecular formula of the one-dimensional Zn functional complex is as follows: { Zn (L) (phen) ((H))2O)]nWherein L isThe hydrogen thiophenedicarboxylic acid, phen, is 1, 10-phenanthroline. The preparation method of the complex comprises the following steps: dissolving zinc nitrate hexahydrate, thiophene-2, 5-dicarboxylic acid and 1, 10-phenanthroline in a mixed solution of distilled water and N, N-Dimethylacetamide (DMA) in a volume ratio of 1:1:1 according to a molar ratio of 1: 1; placing in an oven at 85-95 deg.C for reaction for 48-72 hr, naturally cooling, filtering, and washing the obtained solid with DMA for 2-6 times to obtain white crystalline solid. The preparation method of the complex modified electrode comprises the following steps: and uniformly dispersing the complex in a Nafion solution to obtain a stable suspension, modifying the suspension on the surface of the gold electrode, and naturally drying to obtain the modified electrode. The modified electrode can be used for detecting L-tryptophan.

Description

One-dimensional Zn functional complex and preparation method and application thereof
Technical Field
The invention relates to a Zn functional complex, in particular to a one-dimensional Zn functional complex, a preparation method thereof, a modified electrode constructed by the complex and application of the electrode in L-tryptophan electrochemical detection.
Background
Tryptophan (also called β -indolylalanine, Tryptophan, Typ) is an important nutrient and an important precursor for biosynthesis of auxin in plants, can participate in the renewal of plasma protein in animals to promote the exertion of riboflavin, is also helpful for the synthesis of nicotinic acid and heme, is used as a preventive and therapeutic agent for pellagra medically, and is a hotspot for research in the fields of feed, food, medicine, agriculture and environmental monitoring.
The functional complex is a rapidly developed coordination polymer with inorganic and organic characteristics. The material is another important porous material after zeolite and carbon nano-tube, and has an adjustable framework structure and good performance, so that the material has wide attention in the application fields of energy sources, catalysis, adsorption, energy storage and the like. In recent years, in the electrochemical field, a functional complex is modified on the surface of an electrode by researchers as a novel material to prepare a plurality of electrochemical sensors, and the electrochemical sensors are applied to detection and identification of a plurality of biological and environment-related substances. In 2015, a southern development major school task group takes Cu-MOFs prepared by taking thiophene derivative 2, 5-dicarboxylic acid-3, 4-ethylenedioxythiophene as a ligand as a modified substrate to prepare an electrochemical biosensor, so that the synchronous detection of tryptophan and ascorbic acid is realized, and a good detection effect is obtained. Same year, group of o.m.yaghi topics[20]The Co functional complex based on porphyrin ligand is nanoModifying on electrode after chemical reaction, and adding CO in water system2Electrocatalytic reduction to CO was achieved with a yield of 76%. In view of the potential application prospect of the functional complex in the electrochemical field, the development and design of a novel functional complex applied to the preparation and research of an electrochemical biosensor are one of the hotspots of research of researchers nowadays.
Disclosure of Invention
Based on the background, the invention aims to provide a one-dimensional Zn functional complex and a preparation method and application thereof.
The invention provides a one-dimensional Zn functional complex, which has the molecular formula: { Zn (L) (phen) ((H))2O)]nL is dehydro-thiophene diacid, phen is 1, 10-phenanthroline.
The invention provides a preparation method of a one-dimensional Zn functional complex, which comprises the following steps:
dissolving zinc nitrate hexahydrate, thiophene-2, 5-dicarboxylic acid and 1, 10-phenanthroline in a mixed solution of distilled water and N, N-Dimethylacetamide (DMA) in a volume ratio of 1:1:1 according to a molar ratio of 1: 1; placing in an oven at 85-95 deg.C for reaction for 48-72 hr, naturally cooling, filtering, washing the obtained solid with DMA for 2-6 times to obtain white crystalline solid { Zn (L) (phen) ((H))2O)]n}。
{Zn(L)(phen)(H2O)]nThe preparation method of the modified electrode comprises the following steps:
{Zn(L)(phen)(H2O)]ndispersing in Nafion solution to obtain stable suspension, applying the suspension on the surface of gold electrode, and naturally drying to obtain { Zn (L) ((phen)) (H)2O)]nAnd modifying the electrode.
{Zn(L)(phen)(H2O)]nThe modified electrode can be used for detecting L-tryptophan.
(H) a compound of { Zn (L) (phen)2O)]nThe method for detecting the L-tryptophan by the modified electrode comprises the following steps:
with { Zn (L) (phen) ((H))2O)]nUsing modified electrode as working electrode, Ag+/AgNO3The electrode is used as a reference electrode and a platinum wire electrode is used as an auxiliary electrodeAnd (3) auxiliary electrodes which form a three-electrode system, are connected to an electrochemical workstation, and detect the L-tryptophan in a DMF-BMIMBF4 solution (pH 6.8).
The DMF-BMIMBF4 solution was prepared by mixing N, N-Dimethylformamide (DMF) and 1-butyl-3-methylimidazolium tetrafluoroborate (0.5 mol/L). The pH of the solution was determined by a pH acidimeter.
The invention has the beneficial effects that: the invention prepares the functional complex { Zn (L) (phen) (H) for the first time2O)]nAnd carrying out structural characterization on the functional complex, preparing a novel electrode based on the modification of the functional complex, and detecting the L-tryptophan. The modified electrode has good response to L-tryptophan. The modified electrode is simple to prepare, low in price and obvious in detection effect.
Drawings
FIG. 1 shows { Zn (L) (phen) (H)2O)]nAnalyzing the obtained molecular structure diagram by single crystal X-ray diffraction.
FIG. 2 shows { Zn (L) (phen) (H)2O)]nX-ray powder diffraction pattern of (E) } vs. single crystal simulation data.
FIG. 3 shows { Zn (L) (phen) (H)2O)]nAnd (6) detecting the L-tryptophan by using the modified electrode.
Detailed Description
Example 1: synthesis and characterization of one-dimensional Zn functional complex
Dissolving 0.059g of zinc nitrate hexahydrate, 0.034g of thiophene-2, 5-dicarboxylic acid and 0.036g of phenanthroline in 4mL of distilled water and 4mL of N, N-Dimethylacetamide (DMA) mixed solution, placing the mixture into a closed container, placing the closed container into a 90 ℃ oven for reacting for 48 hours, naturally cooling, filtering, washing the obtained solid with DMA for 2-6 times to obtain a white crystalline solid, namely { Zn (L) (phen) (H)2O)]n}。
The functional complex { Zn (L) (phen) (H)2O)]nCharacterization of properties:
(1) measurement of Single Crystal Structure
The crystal structure is determined by Supernova X-ray single crystal diffractometer and Mo K α ray monochromatized by graphite
Figure BDA0001545536890000031
Is a source of incident radiation, in
Figure BDA0001545536890000033
Diffraction points are collected in a scanning mode, unit cell parameters are obtained through least square method correction, a crystal structure is obtained through direct solution of a difference Fourier electron density diagram by using a SHELXL-97 method, and Lorentz and polarization effect correction are carried out. All H atoms were synthesized by difference Fourier and determined by ideal position calculations. The crystal determination data are shown in table 1.
TABLE 1{ Zn (L) (phen) ((H))2O)]nCrystallographic data of }
Figure BDA0001545536890000032
FIG. 1 shows the compound { Zn (L) (phen) (H)2O)]nThe smallest structural unit diagram obtained by single crystal diffraction analysis shows that the compound molecule contains a zinc ion and a dehydrogenation ligand L-One coordinating water and phenanthroline molecule.
(2) Powder X-ray diffraction measurement
Powder X-ray diffraction data were collected on a Rigaku D/Max-2500 diffractometer at an operating voltage of 40kV and a current of 100mA, using graphite monochromated copper target X-rays as the source of incident radiation during the test. Density data collection Using a 2 θ/θ scan pattern, continuous scans were performed over a range of 3 ° to 60 ° at a scan rate of 8 °/second and a span of 0.02 °/time. Experimental data fitting the program Cerius2 was used and the software Mercury 3.9 was used for powder X-ray diffraction spectrum simulation transformation of single crystal structures.
FIG. 2 shows { Zn (L) (phen) (H)2O)]nPowder X-ray diffraction patterns of the complexes were compared to simulated single crystal data.
Example 2{ Zn (L) (phen) (H)2O)]nPreparation of modified electrodes
Weigh 0.020g { Zn (L) (phen) ((H))2O)]nAdding the complex into 0.4mL of Nafion solution under the ultrasonic condition to obtain whiteA colored suspension. Dropping 10 μ L of the suspension on the surface of a clean gold electrode, and naturally drying for 12 hours to obtain { Zn (L) (phen) ({ H) ((L))2O)]nAnd modifying the electrode.
Example 3{ Zn (L) (phen) (H)2O)]nDetection of L-Tryptophan by modified electrode
The { Zn (L) (phen) (H) obtained by the invention2O)]nAnd the modified electrode is used for detecting the L-tryptophan, and the specific detection method is as follows: the prepared { Zn (L) (phen) (H)2O)]nUsing modified electrode as working electrode, Ag+/AgNO3The electrode is used as a reference electrode, the platinum wire electrode is used as an auxiliary electrode to form a three-electrode system, and the three-electrode system is connected to an electrochemical workstation and is arranged in a DMF-BMIMBF4L-tryptophan was detected in solution (pH 6.8). The modified electrode responded well to L-tryptophan as shown in FIG. 3.

Claims (1)

1. A kind ofL-a method for the detection of tryptophan comprising the steps of:
(1) preparing a one-dimensional Zn functional complex: dissolving zinc nitrate hexahydrate, thiophene-2, 5-dicarboxylic acid and 1, 10-phenanthroline in a mixed solution of distilled water and N, N-dimethylacetamide according to a molar ratio of 1:1: 1; reacting in oven at 85-95 deg.C for 48-72 hr, naturally cooling, filtering, washing the obtained solid with DMA for 2-6 times to obtain white crystalline solid which is one-dimensional Zn functional complex with molecular formula of { Zn (L) (phen) ({ Zn (L)) (H)2O)]n}, wherein: l is dehydrogenated thiophenedioic acid, phen is 1, 10-phenanthroline;
(2) preparing a one-dimensional Zn functional complex modified electrode: uniformly dispersing the one-dimensional Zn functional complex prepared in the step (1) in a Nafion solution to obtain a stable suspension, applying the suspension on the surface of a gold electrode, and naturally drying to obtain a one-dimensional Zn functional complex modified electrode;
(3) taking the one-dimensional Zn functional complex modified electrode prepared in the step (2) as a working electrode, and Ag+/AgNO3The electrode is used as a reference electrode, a platinum wire electrode is used as an auxiliary electrode to form a three-electrode system, and the three-electrode system is connected to an electrochemical workstation and placed in a DMF-BMIMBF4 solutionMiddle pairL-tryptophan.
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