CN103954613A - Electrochemical luminescence system with good biocompatibility - Google Patents

Electrochemical luminescence system with good biocompatibility Download PDF

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CN103954613A
CN103954613A CN201410196909.9A CN201410196909A CN103954613A CN 103954613 A CN103954613 A CN 103954613A CN 201410196909 A CN201410196909 A CN 201410196909A CN 103954613 A CN103954613 A CN 103954613A
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dipeptides
nanotube
concentration range
solution
electrochemical
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CN103954613B (en
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陈旭
黄春秀
杨文胜
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention provides an electrochemical luminescence system with good biocompatibility, and belongs to an electrochemical luminescence system with good biocompatibility. The system comprises: a dipeptide nanotube obtained by self-assembly of a diphenyl alanine dipeptide solution with a concentration range of 0.5-4.0 mg.mL<-1> is used as luminescent substance, and the dipeptide nanotube luminescent substance is modified to the surface of a glassy carbon electrode; co-reaction substance is one of tri-n-propyl amine, ammonium acetate and hexamethylenetetramine, wherein the concentration range of the tri-n-propyl amine is 0.01-20 mmol.L<-1>, the concentration range of the ammonium acetate is 1-20 mmol.L<-1>, and the concentration range of the hexamethylenetetramine is 5-20 mmol.L<-1>; the co-reaction substance exists in a buffer solution, and the pH value of the buffer solution is 6-9. Excited luminescence of the electrochemical luminescent system is analyzed by an electrochemical method. The tubular diameter of the dipeptide nanotube is 400-3000 nm and the length is 80-300 microns. The electrochemical luminescence system has the advantages of good biocompatibility, environmental protection and stable reagent, and can be widely applied to biological analysis.

Description

A kind of electrochemical luminescence system of good biocompatibility
Technical field
The invention belongs to electrochemiluminescence analysis technical field, particularly a kind of electrochemical luminescence system of good biocompatibility.
Background technology
Electrochemiluminescence becomes a noticeable analytical technology in view of its high sensitivity and the wide range of linearity.In recent years, the application acceleration of nano material the application of electrochemiluminescence technology aspect bioanalysis.Semiconductor nano, as CdSe and CdTe, although in being commonly used in electrochemiluminescence research, the toxicity of its heavy metal element inherence has limited their widespread uses in bioanalysis.For maintaining environment good in bioanalysis, the silicon of low toxicity and carbon nano-crystal and gold nanoclusters are attempted being used in electrochemiluminescence analysis.But, their luminous intensity a little less than, also need further raising.Therefore, development is efficient, the electrochemical luminescence system of good biocompatibility to electrochemiluminescence technology the application in bioanalysis significant.
In recent years, two phenylalanine dipeptides, as the simplest dipeptides primitive, attract wide attention.It is the main identification motif of β-starch albumen of alzheimer disease, can be self-assembled into various structure, makes them to provide abundant construction module for numerous application.Dipeptides nano material has good biocompatibility, is easy to the advantage of synthetic and chemical modification.Dipeptides nanotube (Nano Lett.2009,9,3111-3115) is found in nearest research, dipeptides nanosphere (App.Phys.Lett.2009,94,261907) and gel (Adv.Mater.2010,22,2311-2315) in exist quantum confinement phenomenon.These dipeptides self-assembled nano structures are to form (J.Am.Chem.Soc.2010 by nanocrystalline or quantum dot, 132,15632-15636), make this class Bio-Nano-Materials have outstanding electrical and optical properties, eco-friendly clean optical material can be provided.But the application based on dipeptides nanotube in electrochemiluminescence technology have not been reported.
Summary of the invention
The object of the present invention is to provide a kind of electrochemical luminescence system of good biocompatibility, solved the problem such as destruction mechanics of biological tissue and environmental pollution existing in electrochemiluminescence analysis.
Electrochemical luminescence system of the present invention comprises: be 0.5~4.0mgmL by concentration range -1the dipeptides nanotube that obtains of two phenylalanine dipeptide solution self assemblies be luminescent substance, dipeptides nanotube luminescent substance is modified to glass-carbon electrode surface; Coreaction material is Tri-n-Propylamine, ammonium acetate, and the one in hexamethylenetetramine, wherein the concentration range of Tri-n-Propylamine is 0.01~20mmolL -1, the concentration range of ammonium acetate is 1~20mmolL -1, the concentration range of hexamethylenetetramine is 5~20mmolL -1; Coreaction material is present in buffer solution, and the pH value of buffer solution is 6~9.Electrochemical luminescence system stimulated luminescence is analyzed with electrochemical method.Wherein, the tubular diameter of dipeptides nanotube is 400~3000nm, and length is 80~300 μ m.
The preparation process of luminescent substance dipeptides nanotube of the present invention is:
At 20~25 DEG C, the freezing powder of two phenylalanine dipeptides is dissolved in in hexafluoroisopropanol, to be mixed with concentration be 95~105mgmL -1solution, mixes this solution with deionized-distilled water, the concentration range that makes dipeptides is 0.5~4.0mgmL -1.Dipeptides obtains dipeptides nanotube by self assembly.
Coreaction material of the present invention is Tri-n-Propylamine, ammonium acetate, the one in hexamethylenetetramine.Wherein the concentration range of Tri-n-Propylamine is 0.01~20mmolL -1, the concentration range of ammonium acetate is 1~20mmolL -1, the concentration range of hexamethylenetetramine is 5~20mmolL -1.
Buffer solution of the present invention is the phosphate buffered solution of pH6~9.
Electrochemical luminescence system assay method of the present invention adopts three-electrode system, and wherein glass-carbon electrode is working electrode, and platinum filament is to electrode, and silver-silver chloride electrode is contrast electrode.Use electrochemical method to excite before test, need be by nanometer tube modified dipeptides to clean glass-carbon electrode surface, its painting amount at electrode surface is 6 μ L, and scanning potential range is 0~+ 1.4V, and the voltage of photomultiplier is 800V.
Feature of the present invention and effect are:
The invention provides a kind of electrochemical luminescence system of good biocompatibility.The luminescent substance of this electrochemical luminescence system is the dipeptides nanotube that two phenylalanine dipeptide self assemblies form, and coreaction material is Tri-n-Propylamine, ammonium acetate, the one in hexamethylenetetramine.The luminescent system of dipeptides nanotube and amine composition has luminous signal.The advantage of this electrochemical luminescence system good biocompatibility, environmental friendliness, stable reagent, can be widely used in bioanalysis.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the dipeptides nanotube in embodiment 1.
Fig. 2 is the electrochemiluminescence spectrogram of dipeptides nanotube, and emission wavelength is 615nm.
Fig. 3 is the light intensity-voltage curve in embodiment 1, it is blank glass-carbon electrode (a), the nanometer tube modified electrode of dipeptides (b) taking Tri-n-Propylamine in the phosphate buffered solution of coreaction material, carry out that electrochemiluminescence test obtains.
Fig. 4 is the stability of photoluminescence curve map in embodiment 1, be the nanometer tube modified electrode of dipeptides taking Tri-n-Propylamine in the phosphate buffered solution of coreaction material, carry out that electrochemiluminescence test obtains.
Fig. 5 is the light intensity-voltage curve in embodiment 2, is blank glass-carbon electrode (a), the nanometer tube modified electrode of dipeptides (b) taking ammonium acetate in the phosphate buffered solution of coreaction material, carry out that electrochemiluminescence test obtains.
Fig. 6 is the stability of photoluminescence curve map in embodiment 2, be the nanometer tube modified electrode of dipeptides taking ammonium acetate in the phosphate buffered solution of coreaction material, carry out that electrochemiluminescence test obtains.
Fig. 7 is the light intensity-voltage curve in embodiment 3, blank glass-carbon electrode (a), the nanometer tube modified electrode of dipeptides (b) taking hexamethylenetetramine in the phosphate buffered solution of coreaction material, carry out that electrochemiluminescence test obtains.
Fig. 8 is the stability of photoluminescence curve map in embodiment 3, be the nanometer tube modified electrode of dipeptides taking hexamethylenetetramine in the phosphate buffered solution of coreaction material, carry out that electrochemiluminescence test obtains.
Embodiment
At embodiment 1:25 DEG C, the freezing powder of two phenylalanine dipeptides is dissolved in in hexafluoroisopropanol, to be mixed with concentration be 100mgmL -1solution, mixes this solution with deionized-distilled water, the concentration that makes dipeptides is 2.0mgmL -1.Dipeptides obtains dipeptides nanotube by self assembly, and its scanning electron microscope (SEM) photograph as shown in Figure 1.To glass-carbon electrode surface, containing 10mmolL by nanometer tube modified dipeptides -1the 0.1molL of Tri-n-Propylamine -1in the phosphate buffered solution of pH7.4, analyze with electrochemical method stimulated luminescence, light intensity-the voltage curve obtaining as shown in Figure 3, (luminous intensity that Fig. 3 b) records in test fluid is 7500 to the nanometer tube modified glass-carbon electrode of dipeptides, (a) as a comparison, luminous intensity is only 750 to Fig. 3 to blank glass-carbon electrode.As shown in Figure 4, the nanometer tube modified glass-carbon electrode of dipeptides is more stable in test process light intensity for the stability of photoluminescence curve map that this test obtains simultaneously.
At embodiment 2:20 DEG C, the freezing powder of two phenylalanine dipeptides is dissolved in in hexafluoroisopropanol, to be mixed with concentration be 105mgmL -1solution, mixes this solution with deionized-distilled water, the concentration that makes dipeptides is 2.0mgmL -1.Dipeptides obtains dipeptides nanotube by self assembly, is modified glass-carbon electrode surface, is containing 10mmolL -1the 0.1molL of ammonium acetate -1in the phosphate buffered solution of pH7.4, analyze with electrochemical method stimulated luminescence, light intensity-the voltage curve obtaining as shown in Figure 5, (luminous intensity that Fig. 5 b) records in test fluid is 260 to the nanometer tube modified glass-carbon electrode of dipeptides, (Fig. 5 a) as a comparison, does not have luminous signal to blank glass-carbon electrode.As shown in Figure 6, the nanometer tube modified glass-carbon electrode of dipeptides is more stable in test process light intensity for the stability of photoluminescence curve map that this test obtains simultaneously.
At embodiment 3:22 DEG C, the freezing powder of two phenylalanine dipeptides is dissolved in in hexafluoroisopropanol, to be mixed with concentration be 95mgmL -1solution, mixes this solution with deionized-distilled water, the concentration that makes dipeptides is 2.0mgmL -1.Dipeptides obtains dipeptides nanotube by self assembly, is modified glass-carbon electrode surface, is containing 10mmolL -1the 0.1molL of hexamethylenetetramine -1in the phosphate buffered solution of pH7.4, analyze with electrochemical method stimulated luminescence, light intensity-the voltage curve obtaining as shown in Figure 7, (luminous intensity that Fig. 7 b) records in test fluid is 36 to the nanometer tube modified glass-carbon electrode of dipeptides, (Fig. 7 a) as a comparison, does not have luminous signal to blank glass-carbon electrode.As shown in Figure 8, the nanometer tube modified glass-carbon electrode of dipeptides is more stable in test process light intensity for the stability of photoluminescence curve map that this test obtains simultaneously.
At embodiment 4:21 DEG C, the freezing powder of two phenylalanine dipeptides is dissolved in in hexafluoroisopropanol, to be mixed with concentration be 105mgmL -1solution, mixes this solution with deionized-distilled water, the concentration that makes dipeptides is 4.0mgmL -1.Dipeptides obtains dipeptides nanotube by self assembly, is modified glass-carbon electrode surface, is containing 0.01mmolL -1three positive third
The 0.1molL of amine -1in the phosphate buffered solution of pH6.0, analyze with electrochemical method stimulated luminescence, replication three times, the luminous signal mean intensity obtaining is 290.
At embodiment 5:24 DEG C, the freezing powder of two phenylalanine dipeptides is dissolved in in hexafluoroisopropanol, to be mixed with concentration be 100mgmL -1solution, mixes this solution with deionized-distilled water, the concentration that makes dipeptides is 3.0mgmL -1.Dipeptides obtains dipeptides nanotube by self assembly, is modified glass-carbon electrode surface, is containing 5mmolL -1the 0.1molL of hexamethylenetetramine -1in the phosphate buffered solution of pH8.0, analyze with electrochemical method stimulated luminescence, replication three times, the luminous signal mean intensity obtaining is 35.
At embodiment 6:20 DEG C, the freezing powder of two phenylalanine dipeptides is dissolved in in hexafluoroisopropanol, to be mixed with concentration be 95mgmL -1solution, mixes this solution with deionized-distilled water, the concentration that makes dipeptides is 1.0mgmL -1.Dipeptides obtains dipeptides nanotube by self assembly, is modified glass-carbon electrode surface, is containing 15mmolL -1the 0.1molL of ammonium acetate -1in the phosphate buffered solution of pH9.0, analyze with electrochemical method stimulated luminescence, replication three times, the luminous signal mean intensity obtaining is 120.

Claims (2)

1. an electrochemical luminescence system for good biocompatibility, is characterized in that, is 0.5~4.0mgmL by concentration range -1the dipeptides nanotube that obtains of two phenylalanine dipeptide solution self assemblies be luminescent substance, dipeptides nanotube luminescent substance is modified to glass-carbon electrode surface; Coreaction material is Tri-n-Propylamine, ammonium acetate, and the one in hexamethylenetetramine, wherein the concentration range of Tri-n-Propylamine is 0.01~20mmolL -1, the concentration range of ammonium acetate is 1~20mmolL -1, the concentration range of hexamethylenetetramine is 5~20mmolL -1; Coreaction material is present in buffer solution, and the pH value of buffer solution is 6~9; The tubular diameter of dipeptides nanotube is 400~3000nm, and length is 80~300 μ m.
2. electrochemical luminescence system according to claim 1, is characterized in that, described dipeptides nanotube preparation process is:
At 20~25 DEG C, the freezing powder of two phenylalanine dipeptides is dissolved in in hexafluoroisopropanol, to be mixed with concentration be 95~105mgmL -1solution, mixes this solution with deionized-distilled water, the concentration range that makes dipeptides is 0.5~4.0mgmL -1.Dipeptides obtains dipeptides nanotube by self assembly.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105181769A (en) * 2015-08-27 2015-12-23 北京化工大学 Electrochemical cell sensor based on peptide nanotubes/chitosan and preparation method thereof
CN107014886A (en) * 2017-03-08 2017-08-04 常州大学 A kind of application of phenylalanine dipeptide self assembly product of zinc ion induction in electrochemistry chiral Recognition field
CN109288720A (en) * 2017-07-24 2019-02-01 刘崇庆 Deodorant compositions and preparation method thereof
CN109580597A (en) * 2019-01-28 2019-04-05 青岛科技大学 It is a kind of based on the electrochemical luminescence biosensor and its preparation method of DNA nanotube and application
CN110911655A (en) * 2018-09-18 2020-03-24 中信国安盟固利动力科技有限公司 Self-assembled super-fast-charging positive electrode material and lithium ion battery thereof

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LIHI ADLER-ABRAMOVICH ET. AL.: "Self-assembled arrays of peptide nanotubes by vapour deposition", 《NATURE NANOTECHNOLOGY》, vol. 4, 18 October 2009 (2009-10-18), pages 849 - 854, XP055021018, DOI: doi:10.1038/nnano.2009.298 *
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105181769A (en) * 2015-08-27 2015-12-23 北京化工大学 Electrochemical cell sensor based on peptide nanotubes/chitosan and preparation method thereof
CN107014886A (en) * 2017-03-08 2017-08-04 常州大学 A kind of application of phenylalanine dipeptide self assembly product of zinc ion induction in electrochemistry chiral Recognition field
CN109288720A (en) * 2017-07-24 2019-02-01 刘崇庆 Deodorant compositions and preparation method thereof
CN110911655A (en) * 2018-09-18 2020-03-24 中信国安盟固利动力科技有限公司 Self-assembled super-fast-charging positive electrode material and lithium ion battery thereof
CN109580597A (en) * 2019-01-28 2019-04-05 青岛科技大学 It is a kind of based on the electrochemical luminescence biosensor and its preparation method of DNA nanotube and application

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