CN106770569A - A kind of application of gold nano of N acetyl L cysteines protection and application process - Google Patents

A kind of application of gold nano of N acetyl L cysteines protection and application process Download PDF

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Publication number
CN106770569A
CN106770569A CN201611092358.7A CN201611092358A CN106770569A CN 106770569 A CN106770569 A CN 106770569A CN 201611092358 A CN201611092358 A CN 201611092358A CN 106770569 A CN106770569 A CN 106770569A
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acetyl
cysteines
protection
gold nano
tyrosine
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郭玉晶
刘志广
王丽
任宏瑛
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Shanxi University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3277Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
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Abstract

The invention belongs to electrochemical sensor and molecular recognition technical field, and in particular to a kind of application of gold nano of N acetyl L cysteines protection and application process.The application process of the gold nano of N acetyl L cysteines protection of the present invention, comprises the following steps:A. the gold nano solution of N acetyl L cysteines protection is prepared, glassy carbon electrode surface is deposited on using cyclic voltammetry, obtain the glass-carbon electrode of the gold nano modification of N acetyl L cysteines protection;The glass-carbon electrode NALC Au/GCE of the gold nano modification that b. obtained N acetyl L cysteines in step a are protected are rested in the L tyrosine or D tyrosine solutions that pH is 6~7; electrode surface is deposited on using cyclic voltammetry, the gold nano of N acetyl L cysteines protection and the glass-carbon electrode NALC Au/GCE L/D Tyr of tyrosine modification is obtained;The glass-carbon electrode NALC Au/GCE L/D Tyr of the protection of N acetyl L cysteines c. will be obtained in step b gold nano and tyrosine modification are circulated volt-ampere and electrochemical impedance chiral Recognition in the solution of the potassium ferricyanide/KCl.

Description

A kind of application of gold nano of N- acetyl L-cysteines protection and application process
Technical field
The invention belongs to electrochemical sensor and molecular recognition technical field, and in particular to a kind of N- acetyl L-cysteines The application of the gold nano of protection and application process.
Background technology
Chiral Recognition is a common phenomenon of chemistry, biology, medicine.Chiral molecules is to possess identical Chemical property and physical property, but they are but very different in terms of bioactivity and pharmacology, even completely phase Anti- effect.Such as:Aspartic acid S types are bitter tastes, and R types are sweet tastes;Salbutamol S types can be serious teratogenesis, and R types It is sedative, the morning sickness reaction of gravid woman can be alleviated.Ketamine S types are anesthetic, are used as anesthesia before clinic operation, and R Type is psychedelic, is prohibitted the use of;Ethambutol S types can treat tuberculosis, and R types can blinding.Tyrosine, tyrosine L-type for another example It is human body nonessential amino acid, melancholia and other mental diseases is may result in during shortage, and sister can be increased if excess The probability that chromosome is exchanged, the healthy development of influence children of future generation.And tyrosine D types are used as one kind of non-protein amino acid, There is important meaning in terms of the structure and running function of investigation protein.Thus chiral Recognition enantiomter has important Meaning.
At present, chiral Recognition method mainly has following several:Capillary electrophoresis, high performance liquid chromatography, fluorescence spectrum Detection method and electrochemical method.Wherein capillary electrophoresis, high-efficient liquid phase chromatogram technique analysis high cost, analysis time are long, unfavorable In quick detection;Fluorescence spectrum detection method detection range is narrow.It would therefore be highly desirable to develop a kind of simple, quick, sensitive chiral Recognition Method.
The content of the invention
The purpose of the present invention is application and the application process of a kind of gold nano of N- acetyl L-cysteines protection.
The technical scheme is that:
A kind of application of the gold nano of N- acetyl L-cysteines protection, for electrochemical method chiral Recognition tyrosine.
The application process of the gold nano of N- acetyl L-cysteines protection of the present invention, comprises the following steps:
A. it is the KCl solution of 0.1mol/L to prepare solvent, and pH is the gold nano of 6~7 N- acetyl L-cysteines protection Solution, glassy carbon electrode surface is deposited on using cyclic voltammetry, obtains the gold nano modification of N- acetyl L-cysteines protection Glass-carbon electrode NALC-Au/GCE;
B. by the glass-carbon electrode NALC-Au/ of the gold nano modification of obtained N- acetyl L-cysteines protection in step a GCE is rested in the TYR that pH is 6~7 or D-Tyrosine solution, and electrode surface is deposited on using cyclic voltammetry, is obtained The gold nano of N- acetyl L-cysteines protection and the glass-carbon electrode NALC-Au/GCE-L-/D-Tyr of tyrosine modification;
C. by the gold nano of obtained N- acetyl L-cysteines protection in step b and the glass-carbon electrode of tyrosine modification NALC-Au/GCE-L-/D-Tyr is circulated volt-ampere and electrochemical impedance chiral Recognition in the solution of the potassium ferricyanide/KCl.
Further, the concentration of the gold nano solution of the N- acetyl L-cysteines protection in step a of the present invention is 10~100mmol/L, to being made up of disodium hydrogen phosphate and potassium dihydrogen phosphate, pH is 6~7 to the buffering of pH value of solution.
Gold nano -0.75~1.6V of deposition voltage of N- acetyl L-cysteines protection, sinks in step a of the present invention The product number of turns 2~8 is enclosed.
TYR or D-Tyrosine solution concentration are 10~769mmol/L in step b of the present invention, pH value of solution To being made up of disodium hydrogen phosphate and potassium dihydrogen phosphate, pH is 4.07~7 to buffering.
The sedimentation potential of TYR or D-Tyrosine solution is 0.4~1V in step b of the present invention, deposits the number of turns It is 1~6 circle.
The concentration of potassium ferricyanide solution is 1~10mmol/L in step c of the present invention.
The present invention uses above-mentioned technical proposal, the method based on electrochemical impedance, carries out the knowledge of tyrosine enantiomter Not, experiment proves the method preparation process is simple, and testing cost is cheap, good stability.
Brief description of the drawings
Fig. 1 is for the glass-carbon electrode of the gold nano modification of N- acetyl L-cysteines protection in embodiment 1 and to TYR Or the cyclic voltammogram of D-Tyrosine enantiomer identification;A in Fig. 1:GCE, b:The gold nano of N- acetyl L-cysteines protection is repaiied The glass-carbon electrode of decorations, c:The gold nano of N- acetyl L-cysteines protection and the glass-carbon electrode of L-Tyr modifications, d:N- acetyl L- half The gold nano of cystine protection and the glass-carbon electrode of D-Tyr modifications;
Fig. 2 is for the glass-carbon electrode of the gold nano modification of N- acetyl L-cysteines protection in embodiment 2 and to TYR Or the impedance diagram of D-Tyrosine enantiomer identification, from Figure 2 it can be seen that the impedance value of D type tyrosine is significantly greater than the resistance of L-type tyrosine Anti- value;A in Fig. 2:GCE, b:The glass-carbon electrode of the gold nano modification of N- acetyl L-cysteines protection, c:The Guang ammonia of N- acetyl L- half The gold nano of acid protection and the glass-carbon electrode of L-Tyr modifications, d:The gold nano of N- acetyl L-cysteines protection and D-Tyr modifications Glass-carbon electrode;
Fig. 3 is in embodiment 3, the gold nano of N- acetyl L-cysteines protection deposits influence of the number of turns to electrode modification;
Fig. 4 is in embodiment 3, tyrosine solution deposits the influence of the chiral identification tyrosine of the number of turns;
Fig. 5 be embodiment 4 in, tyrosine solution pH it is chiral identification tyrosine influence;
Fig. 6 be embodiment 5 in, tyrosine solution concentration it is chiral identification tyrosine influence.
Specific embodiment
Embodiment 1
The application process of the gold nano of N- acetyl L-cysteines protection:
Prepare the gold nano of N- acetyl L-cysteines protection:
0.227g N- acetyl L-cysteines are weighed, it is 6 to be dissolved in 10mL volume ratios:1 glacial acetic acid solution of methyl alcohol one In.0.182g gold chlorides are weighed, it is 6 to be dissolved in 10mL volume ratios:In 1 glacial acetic acid solution of methyl alcohol one.Chlorauric acid solution is turned Move in the round-bottomed flask of 100mL, ice bath stirring adds down the glacial acetic acid solution of N- acetyl L-cysteines methyl alcohol one for having prepared, When solution is changed into orange from golden yellow, EtOH Sonicate dispersions of the 5mL containing sodium borohydride (0.35g) is disposably rapidly joined molten Liquid, reacts 30min, adds 50mL acetone to stop reaction.Precipitation is collected by centrifugation.With proper amount of acetone and water by above-mentioned sediment repeatedly Dissolving, precipitation, centrifugation, washing, then dialyse to remove foreign ion present in solution, nitrogen with the bag filter of 8000-14000Da 4 DEG C of Refrigerator stores are placed in after air-blowing is dry.
A. (solvent is 0.1mol/LKCl, pH=to the gold nano solution 55mmol/L of preparation N- acetyl L-cysteines protection 6.53) glassy carbon electrode surface, is deposited on using cyclic voltammetry, deposition voltage is -0.75~1.6V, and the deposition number of turns 6 is enclosed, obtained The glass-carbon electrode of the gold nano modification of N- acetyl L-cysteines protection, from Fig. 1 (b), Fig. 2 (b), the Guang ammonia of N- acetyl L- half Successfully glassy carbon electrode surface is arrived in modification to the gold nano of acid protection.
B. in the electrode that step (a) is obtained being rested on into TYR or D-Tyrosine solution (pH=6.53), using following TYR or D-Tyrosine are deposited on electrode surface by ring voltammetry, obtain N- acetyl L-cysteines protection gold nano and The modified electrode of tyrosine.From Fig. 1 (c), 1 (d) and Fig. 2 (c), 2 (d), successfully electrode surface is arrived in modification to tyrosine.
C. the gold nano of obtained N- acetyl L-cysteines protection in step (b) and the modified electrode of tyrosine are placed in In the 5mmol/L potassium ferricyanides/0.1mol/L KCl solution, characterized using cyclic voltammetry and electrochemical impedance.By Fig. 2 (c), 2 D () understands, D type tyrosine impedance values are apparently higher than L-type tyrosine.Cyclic voltammetry potential range is -0.2~0.6V, sweeps speed It is 0.1V/s.Electrode with Electrochemical Impedance Spectroscopy frequency range is 0.1~6105Hz, amplitude is 0.01V.
Embodiment 2
The gold nano for investigating the protection of N- acetyl L-cysteines deposits the influence of the number of turns.
The preparation of the gold nano of N- acetyl L-cysteines protection and the modified electrode of tyrosine is with embodiment one, NALC- The Au deposition number of turns is respectively adopted 2,3,5,6,7,8 circles, and its result is shown in Fig. 3, it is seen that when the NALC-Au deposition number of turns is 6 circle, formed The thickness of film of glass-carbon electrode modified electrode of gold nano modification of N- acetyl L-cysteines protection be best suitable for, electrode surface The exposed area of film it is maximum, more can be combined with TYR or D-Tyrosine.
Embodiment 3
Investigate difference of the tyrosine deposition number of turns to tyrosine enantiomer recognition capability.
The preparation of the gold nano of N- acetyl L-cysteines protection and the modified electrode of tyrosine is with embodiment one, NALC- The Au deposition number of turns is respectively adopted 1,2,3,4,5 circles, carries out the identification of tyrosine enantiomer, and its result is shown in Fig. 4, is in the deposition number of turns During 3 circle, the glass-carbon electrode of the gold nano modification of N- acetyl L-cysteines protection is best to tyrosine enantiomer recognition capability.
Embodiment 4
Tyrosine is investigated under different pH, the gold nano modified glassy carbon electrode of N- acetyl L-cysteines protection is extremely to junket ammonia The difference of sour enantiomer recognition capability.
The preparation of the gold nano of N- acetyl L-cysteines protection and the modified electrode of tyrosine is with embodiment one, tyrosine Solution is respectively adopted pH4.07, pH5.13, pH5.66, pH5.91, pH6.53, pH7.00, carries out the identification of tyrosine enantiomer, Its result is shown in Fig. 5, it is seen that when pH is 6.53, and the glass-carbon electrode of the gold nano modification of N- acetyl L-cysteines protection is to junket ammonia Sour enantiomer recognition capability difference is maximum.
Embodiment 5
Tyrosine is investigated under various concentrations, the gold nano modified glassy carbon electrode of N- acetyl L-cysteines protection is extremely to junket The difference of propylhomoserin enantiomer recognition capability.
The preparation of the gold nano of N- acetyl L-cysteines protection and the modified electrode of tyrosine is with embodiment one, tyrosine Concentration is respectively adopted 10,25,50,164,323,476,769mmol/L carry out the identification of enantiomer, its result is shown in Fig. 6, in junket ammonia The concentration of acid is 245mmol/L, and the glass-carbon electrode of the gold nano modification of N- acetyl L-cysteines protection is to tyrosine enantiomer Recognition capability is best.

Claims (7)

1. a kind of application of the gold nano of N- acetyl L-cysteines protection, it is characterised in that for electrochemical method chiral Recognition Tyrosine.
2. described in claim 1 N- acetyl L-cysteines protection gold nano application application process, it is characterised in that Comprise the following steps:
A. it is the KCl solution of 0.1mol/L to prepare solvent, and pH is the gold nano solution of 6~7 N- acetyl L-cysteines protection, Glassy carbon electrode surface is deposited on using cyclic voltammetry, the glass carbon electricity of the gold nano modification of N- acetyl L-cysteines protection is obtained Pole NALC-Au/GCE;
B. it is the glass-carbon electrode NALC-Au/GCE of the gold nano modification of obtained N- acetyl L-cysteines protection in step a is quiet Put in the TYR or D-Tyrosine solution that pH is 6~7, electrode surface is deposited on using cyclic voltammetry, obtain N- second The gold nano of acyl Cys protection and the glass-carbon electrode NALC-Au/GCE-L-/D-Tyr of tyrosine modification;
C. by the gold nano of obtained N- acetyl L-cysteines protection in step b and the glass-carbon electrode NALC- of tyrosine modification Au/GCE-L-/D-Tyr is circulated volt-ampere and electrochemical impedance chiral Recognition in the solution of the potassium ferricyanide/KCl.
3. the application process of the gold nano of N- acetyl L-cysteines according to claim 2 protection, it is characterised in that institute The concentration for stating the gold nano solution that the N- acetyl L-cysteines in step a are protected is 10~100mmol/L, the buffering of pH value of solution To being made up of disodium hydrogen phosphate and potassium dihydrogen phosphate, pH is 6~7.
4. the application process of the gold nano of N- acetyl L-cysteines according to claim 2 protection, it is characterised in that institute Gold nano -0.75~1.6V of deposition voltage of N- acetyl L-cysteines protection in the step of stating a, the deposition number of turns 2~8 is enclosed.
5. the application process of the gold nano of N- acetyl L-cysteines according to claim 2 protection, it is characterised in that institute TYR or D-Tyrosine solution concentration are 10~769mmol/L in the step of stating b, and the buffering of pH value of solution is to by phosphoric acid hydrogen two Sodium and potassium dihydrogen phosphate are constituted, and pH is 4.07~7.
6. the application process of the gold nano of N- acetyl L-cysteines according to claim 2 protection, it is characterised in that institute The sedimentation potential of TYR or D-Tyrosine solution is 0.4~1V in the step of stating b, and the deposition number of turns is 1~6 circle.
7. the application process of the gold nano of N- acetyl L-cysteines protection according to claim 2, it is characterised in that The concentration of potassium ferricyanide solution is 1~10mmol/L in described step c.
CN201611092358.7A 2016-12-01 2016-12-01 A kind of application of gold nano of N acetyl L cysteines protection and application process Pending CN106770569A (en)

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CN108490063A (en) * 2018-04-13 2018-09-04 西北大学 A kind of biological thiol electrochemical sensor and the preparation method and application thereof
CN112143494A (en) * 2020-09-24 2020-12-29 常州大学 Molybdenum disulfide quantum dot-chiral gold nanoparticle assembly and preparation method and application thereof
CN112834379A (en) * 2021-01-22 2021-05-25 盐城工学院 Cysteine chiral recognition sensor
CN113237934A (en) * 2021-05-24 2021-08-10 常州大学 Chiral silver sulfide quantum dot/few-layer carbon nitride compound for electrochemiluminescence chiral recognition and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108490063A (en) * 2018-04-13 2018-09-04 西北大学 A kind of biological thiol electrochemical sensor and the preparation method and application thereof
CN112143494A (en) * 2020-09-24 2020-12-29 常州大学 Molybdenum disulfide quantum dot-chiral gold nanoparticle assembly and preparation method and application thereof
CN112143494B (en) * 2020-09-24 2022-09-02 常州大学 Molybdenum disulfide quantum dot-chiral gold nanoparticle assembly and preparation method and application thereof
CN112834379A (en) * 2021-01-22 2021-05-25 盐城工学院 Cysteine chiral recognition sensor
CN113237934A (en) * 2021-05-24 2021-08-10 常州大学 Chiral silver sulfide quantum dot/few-layer carbon nitride compound for electrochemiluminescence chiral recognition and preparation method thereof
CN113237934B (en) * 2021-05-24 2024-04-09 常州大学 Chiral silver sulfide quantum dot/few-layer carbon nitride compound capable of being used for electrochemiluminescence chiral recognition and preparation method thereof

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Application publication date: 20170531