CN105044178A - Chiral recognition to tryptophan enantiomer containing zinc ion by chiral sensor based on chitosan/sodium alginate - Google Patents
Chiral recognition to tryptophan enantiomer containing zinc ion by chiral sensor based on chitosan/sodium alginate Download PDFInfo
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Abstract
The invention relates to chiral recognition to a tryptophan enantiomer containing zinc ions by a chiral sensor based on chitosan/sodium alginate. The chiral recognition includes the following steps: (1) preparing a chitosan-modified glassy carbon electrode (CS/GCE); (2) preparing a chitosan/sodium alginate modified electrode (CS/SA/GCE), and (3) recognizing Zn(II)-L-/D-Trp. The CS/SA electrode is simple in operation, can save time and is pollution free. A result proves that the CS/SA-modified glassy carbon electrode has a high-effective recognition capability to the Zn(II)-L-/D-Trp, wherein the potential difference of the Zn(II)-L-/D-Trp can reach 136 mV.
Description
Technical field
The present invention relates to based on glass-carbon electrode substrates shitosan (CS), self assembly sodium alginate (SA) again, obtain CS/SA/GCE modified electrode, adopt DPV to carry out Selective recognition to Zn (II)-L-/D-Trp, belong to electrochemical sensor and molecular recognition field.
Background technology
Chipal compounds and life process closely bound up, different chiral isomers biologically active in vivo, pharmacological action, metabolic processes etc. have obvious difference, therefore development is simple, and accurately, chiral Recognition method becomes the popular direction of chiral analysis in recent years fast.Recent years, the research of chiral sensor has achieved and has developed faster, and wherein electrochemical sensor is because its preparation is simple, cost is low, recognition efficiency advantages of higher, is used for identifying that chiral material has researching value very widely.
The natural polymer that polysaccharide is made up of monose, they are extensively present in plant, animal and microorganism cultures, have multiple important function.Glucide has the bio-pharmaceutical such as anti-inflammatory, antiviral, radioresistance, Nucleic acid and is worth.Nearest carbohydrate is rapid in the development of supramolecular chemistry, and as Tao Yongxin etc. modifies natural beta-schardinger dextrin-on L-glutamic acid, carried out galvanochemistry identify fast L/D-tryptophane, the oxidation peak current ratio of L/D-tryptophane reaches 2.30; YukiMatsuoka etc. carry out chiral separation by design dna-chitosan ultrafiltration membrane to phenylalanine, and experiment finds that D-phenylalanine is preferentially through this ultra filtration membrane etc., and this opens new way for chipal compounds identification.Shitosan has good adsorbability, film forming and permeability, fiberizability, hydroscopicity and moisture retention.Shitosan macromolecular chain is dispersed with many hydroxyls, amino, also have some N-acetylaminos, they can be formed in various molecule and intermolecular ydrogen bonding, make shitosan have the effects such as ion-exchange, ion chelating, absorption to many ions, organism and biomolecule, Chitosan-phospholipid complex can be used as chiral Recognition material simultaneously.Sodium alginate is a kind of natural polysaccharide, has good film forming, and its compound substance is widely used in food additives.Report, SA and APTES silane is by molecular engram hybridized film Selective Separation isomers of phenylalanine, and this shows the potential application of SA in chiral Recognition a few days ago.Water, amino acid, polysaccharide, metallic ion play a part very important in human body and animal life activity.Their interphase interaction, joint effect whole life system.Therefore the present invention adopts glass-carbon electrode substrates shitosan (CS), self assembly sodium alginate (SA) again, obtain CS/SA/GCE modified electrode, adopt differential pulse voltammetry (DPV) to carry out Selective recognition to (Zn (II)-L-/D-Trp), disclose the mutual relationship between them.
Summary of the invention
For the feature in background technology, the glass-carbon electrode (CS/SA/GCE) that the object of the invention is to be modified by shitosan/sodium alginate carries out Selective recognition to Zn (II)-L-/D-Trp.
The technical solution adopted for the present invention to solve the technical problems is: glass-carbon electrode substrates CS, self assembly SA again, obtain glass-carbon electrode (CS/SA/GCE) modified electrode that shitosan/sodium alginate is modified, adopt DPV to carry out Selective recognition to Zn (II)-L-/D-Trp.Comprise the following steps:
A, prepare chitosan-modified glass-carbon electrode (CS/GCE): preparation CS solution (solvent is 0.1 ~ 0.3MHCl, pH=1.0 ~ 2.0), adopt potentiostatic electrodeposition in glassy carbon electrode surface, obtain CS/GCE modified electrode.
B, preparation CS/SA/GCE modified electrode: the CS/GCE modified electrode prepared in step a is rested on 18 ~ 36h in SA solution (pH=6.4), obtains CS/SA/GCE modified electrode.
C, identification to Zn (II)-L-/D-Trp: adopt differential pulse method to identify L-/D-Trp, CS/SA/GCE modified electrode obtained in step b is rested in 20 ~ 30mLZn (II)-L-/D-Trp solution (time of repose 300s ~ 1200s), within the scope of the electrochemical window of 0.4V ~ 1.0V (vs.SCE), DPV is carried out with the speed of sweeping of 0.1 ~ 0.5V/s, the complete rear modified electrode of each survey carries out repeatedly electric potential scanning to stable in 20 ~ 30mL blank solution (0.1 ~ 0.3MKClpH=6.4), recovers electrode activity.
Further, in step a, the concentration of CS is 2 ~ 3g/L.
Further, in step a, sedimentation potential is-0.3 ~-0.7V.
Further, in step a, sedimentation time is 90 ~ 210s.
Further, in step b, the concentration of SA is 1.8 ~ 2.2g/L.
Further, in step c, the concentration of Zn (II) is 0.04 ~ 0.06mM.
Further, in step c, the concentration of L-/D-Trp is 0.1 ~ 0.5mM.
The invention has the beneficial effects as follows: the invention provides a kind of chiral sensor based on shitosan/sodium alginate, if this sensor main is passed through shitosan potentiostatic electrodeposition in glassy carbon electrode surface, sensor prepared by self assembly sodium alginate again, preparation method is simple, raw material is cheaply easy to get, safety non-toxic, and detection sensitivity is high.During chiral Recognition, only this sensor need be immersed in a period of time in the Freamine Ⅲ of supporting electrolyte configuration, then obtain chiral Recognition result by Electrochemical Detection, simple to operate, save time, and there is higher detection sensitivity.Chiral sensor of the present invention can identify the tryptophane isomeride containing Zn (II) efficiently.Experiment shows, this chiral sensor has efficient recognition capability to Zn (II)-L-/D-Trp, and its oxidation peak potential difference (PD) can reach 136mV.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, this experiment is further illustrated.
Fig. 1 is the cyclic voltammogram of each modified electrode in embodiment one.
Fig. 2 be in embodiment two time of repose on the impact of recognition efficiency.
Fig. 3 is that the pH of Zn (II)-L-/D-Trp in embodiment three is on the impact of recognition efficiency.
Fig. 4 is the impact of content on recognition efficiency of L-Trp in embodiment four.
Fig. 5 be in comparative example one CS/SA/GCE modified electrode on the impact identified L-/D-Trp with or without Zn (II).
Embodiment
The invention will be further described in conjunction with specific embodiments now, and following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment one:
(1) prepare shitosan (CS) solution (solvent is 0.1MHCl), adopt constant potential that CS is deposited on glassy carbon electrode surface, deposition voltage is-0.3 ~-0.7V, and sedimentation time is 150s, obtains CS/GCE modified electrode.
(2) electrode that step 1 prepares is rested on 18 ~ 36h in SA solution, obtain CS/SA/GCE modified electrode.
(3) rest in potassium ferricyanide solution by the electrode that step 1, step 2 prepare, adopt cyclic voltammetry to characterize, potential range is-0.2 ~ 0.6V, sweeps speed for 0.1v/s.
Embodiment two:
Under investigating different time of repose, the difference that the glass-carbon electrode that CS/SA/GCE modifies identifies Zn (II)-L-/D-Trp.Therefore, adopt the time of repose of 150s, 300s, 450s, 600s, 900s, 1200s respectively, carry out the identification of Zn (II)-L-/D-Trp, it the results are shown in Figure 2, as seen upon standing between when being 600s, recognition efficiency is maximum.
Embodiment three:
Under investigating different pH, the difference that the glass-carbon electrode that CS/SA/GCE modifies identifies Zn (II)-L-/D-Trp.Therefore, regulate pH to be 3,5,7,9,11 respectively, carry out the identification of Zn (II)-L-/D-Trp, it the results are shown in Figure 3, along with the increase spike potential difference of pH is larger, when pH reaches 7.0, spike potential difference is larger, reaches balance afterwards after the larger spike potential of pH reduces.When pH is 3 ~ 6, tryptophane positively charged, repel each other with the amino positive electricity on Zn (II), CS, current potential is little; And pH is when being 6 ~ 11, there is ligand exchange in Zn (II)-Trp and SA/CS, causes current potential to increase, pH>7, and modified electrode adsorbs L-/D-Trp and increases simultaneously, and potential change not quite, reaches balance.
Embodiment four:
In order to investigate the application of CS/SA/GCE modified electrode in Zn (II)-L-/D-Trp solution.In the mixed system of L-/D-Trp, obtained different current potentials by the content changing L-Trp thus simulated linear equation, we adopt the L-Trp solution of 0%, 10%, 30%, 40%, 50%, 60%, 80%, 100%, and it the results are shown in Figure 4.By linear equation, we can determine the content of L-Trp, D-Trp in mixed system substantially.
Comparative example one:
(1) CS/SA/GCE modified electrode is prepared according in embodiment one step 2, this electrode is rested on 600s in L-/D-Trp solution, within the scope of the electrochemical window of 0.4V ~ 1.0V (vs.SCE), DPV is carried out with the speed of sweeping of 0.1 ~ 0.5V/s, the complete rear modified electrode of each survey carries out repeatedly electric potential scanning to stable in 25mL blank solution (0.1MKClpH=6.4), recovers electrode activity.
It the results are shown in Figure 5, and we can find out, CS/SA/GCE modified electrode has better recognition capability to the Tryptophan enantiomer containing zinc ion.Because CS/SA can form coordination compound with Zn (II), tryptophane, Zn (II) is conducive to, with CS/SA, ligand exchange occurs, and forms quaternary coordination system, thus improves its recognition capability.
Claims (4)
1. glass-carbon electrode substrates shitosan (CS), self assembly sodium alginate (SA) again, obtain CS/SA/GCE modified electrode, adopt differential pulse voltammetry (DPV) to carry out Selective recognition to Zn (II)-L-/D-Trp, step is as follows:
A, prepare chitosan-modified glass-carbon electrode (CS/GCE): preparation CS solution (solvent is 0.1 ~ 0.3MHCl, pH=1.0 ~ 2.0), adopt potentiostatic electrodeposition in glassy carbon electrode surface, obtain CS/GCE modified electrode.
B, preparation CS/SA/GCE modified electrode: the CS/GCE modified electrode prepared in step a is rested on 18 ~ 36h in SA solution (pH=6.4), obtains CS/SA/GCE modified electrode.
C, identification to Zn (II)-L-/D-Trp: adopt differential pulse method to identify Tryptophan enantiomer, CS/SA/GCE modified electrode obtained in step b is rested in 20 ~ 30mLZn (II)-L-/D-Trp solution (time of repose 300s ~ 1200s), within the scope of the electrochemical window of 0.4V ~ 1.0V (vs.SCE), carry out DPV with the speed of sweeping of 0.1 ~ 0.5V/s, surveyed rear modified electrode at every turn and swept in 20 ~ 30mL blank solution (0.1 ~ 0.3MKClpH=6.4) and surely recover electrode activity.
2. glass-carbon electrode substrates CS according to claim 1, self assembly SA again, obtain CS/SA/GCE modified electrode, DPV is adopted to carry out Selective recognition to Zn (II)-L-/D-Trp, it is characterized in that: in described step a, the concentration of CS is 2 ~ 3g/L, sedimentation potential is-0.3 ~-0.7V, and sedimentation time is 90 ~ 210s, and temperature of reaction is 25 ~ 30 DEG C.
3. glass-carbon electrode substrates CS according to claim 1, self assembly SA again, obtain CS/SA/GCE modified electrode, DPV is adopted to carry out Selective recognition to Zn (II)-L-/D-Trp, it is characterized in that: in described step b, the concentration of SA is 1.8 ~ 2.2g/L, temperature of reaction is 25 ~ 30 DEG C.
4. glass-carbon electrode substrates CS according to claim 1, self assembly SA again, obtain CS/SA/GCE modified electrode, DPV is adopted to carry out Selective recognition to Zn (II)-L-/D-Trp, it is characterized in that: in described step c, the concentration of Zn (II) is 0.04 ~ 0.06mM, the concentration of L-/D-Trp is 0.1 ~ 0.5mM, and temperature of reaction is 25 ~ 30 DEG C.
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Cited By (7)
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| CN105628765A (en) * | 2016-02-29 | 2016-06-01 | 常州大学 | Preparation of sodium alginate/beta-cyclodextrin-based chiral sensor and chiral recognition of tryptophan through same |
| CN106018517A (en) * | 2016-05-16 | 2016-10-12 | 常州大学 | Preparation of tartaric acid-graphene quantum dot composite film modified electrode and application in tryptophan enantiomer recognition |
| CN106908507A (en) * | 2017-02-22 | 2017-06-30 | 常州大学 | A kind of preparation and its application of phenylalanine dipeptide Chitosan Composites |
| CN107238643A (en) * | 2017-05-08 | 2017-10-10 | 常州大学 | The preparation of the silicon dioxide modified indium-tin oxide electrode of branching shape molecular engram |
| CN108645900A (en) * | 2018-04-18 | 2018-10-12 | 常州大学 | A kind of preparation method for the glutathione modified electrode can be applied to electrochemistry chiral Recognition |
| CN108732231A (en) * | 2018-04-09 | 2018-11-02 | 中南大学 | The chitosan-modified glass-carbon electrode of soluble starch-and its application |
| CN108872339A (en) * | 2018-04-20 | 2018-11-23 | 常州大学 | A kind of molecular engram sodium alginate/manganese dioxide modified electrode preparation method for electrochemical recognition cysteine enantiomer |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105628765A (en) * | 2016-02-29 | 2016-06-01 | 常州大学 | Preparation of sodium alginate/beta-cyclodextrin-based chiral sensor and chiral recognition of tryptophan through same |
| CN105628765B (en) * | 2016-02-29 | 2018-10-16 | 常州大学 | A method of the preparation based on sodium alginate/beta-cyclodextrin chiral sensor and its tryptophan chiral Recognition |
| CN106018517A (en) * | 2016-05-16 | 2016-10-12 | 常州大学 | Preparation of tartaric acid-graphene quantum dot composite film modified electrode and application in tryptophan enantiomer recognition |
| CN106018517B (en) * | 2016-05-16 | 2018-08-14 | 常州大学 | The preparation of a kind of complex film modified electrode of tartaric acid-graphene quantum dot and applied to identification Tryptophan enantiomer |
| CN106908507A (en) * | 2017-02-22 | 2017-06-30 | 常州大学 | A kind of preparation and its application of phenylalanine dipeptide Chitosan Composites |
| CN107238643A (en) * | 2017-05-08 | 2017-10-10 | 常州大学 | The preparation of the silicon dioxide modified indium-tin oxide electrode of branching shape molecular engram |
| CN107238643B (en) * | 2017-05-08 | 2019-06-04 | 常州大学 | The preparation of the silicon dioxide modified indium-tin oxide electrode of branching shape molecular engram |
| CN108732231A (en) * | 2018-04-09 | 2018-11-02 | 中南大学 | The chitosan-modified glass-carbon electrode of soluble starch-and its application |
| CN108645900A (en) * | 2018-04-18 | 2018-10-12 | 常州大学 | A kind of preparation method for the glutathione modified electrode can be applied to electrochemistry chiral Recognition |
| CN108872339A (en) * | 2018-04-20 | 2018-11-23 | 常州大学 | A kind of molecular engram sodium alginate/manganese dioxide modified electrode preparation method for electrochemical recognition cysteine enantiomer |
| CN108872339B (en) * | 2018-04-20 | 2020-05-26 | 常州大学 | Preparation method of molecularly imprinted sodium alginate/manganese dioxide modified electrode for electrochemically identifying cysteine enantiomer |
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