CN1379239A - Electrochemical luminescence detector for solid nano gold sol-gel and its preparing process - Google Patents
Electrochemical luminescence detector for solid nano gold sol-gel and its preparing process Download PDFInfo
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- CN1379239A CN1379239A CN 02116460 CN02116460A CN1379239A CN 1379239 A CN1379239 A CN 1379239A CN 02116460 CN02116460 CN 02116460 CN 02116460 A CN02116460 A CN 02116460A CN 1379239 A CN1379239 A CN 1379239A
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Abstract
An electrochemical luminous detector of nanometre solid gold sol-gel uses metal complex as the electrochemical luminous molecule. Its structural formula is M(P)x, where M is Ru, P is ligand chosen from pyridine, drjoyridine, etc., and x=3. Its advantages are high stability of electrode, high detection sensitivity and good linearity relationship.
Description
Technical field: the invention belongs to electrochemical luminescence detector for solid nano gold sol-gel and preparation method.
Background technology: electrochemiluminescence detection technique (ECL) is a method the sensitiveest in the electrochemical measuring technique, is used for the detection of drug molecule, amino acid, polypeptide, protein and nucleic acid.Wherein studying and use more is the electrochemiluminescsystem system of tris (bipyridine) ruthenium.Its advantage is the detection sensitivity height, the range of linearity is wide, and favorable reproducibility is because tris (bipyridine) ruthenium reagent is comparatively expensive, therefore tris (bipyridine) ruthenium being fixed on that the preparation solid electrochemical luminescence detector is the emphasis of research always on the electrode, also is the key issue that ECL is applied to conventional sense.H.D.Abruna and A.J.Bard have delivered at J.Am.Chem.Soc.104 (1982) 2641 and have adopted the electropolymerization method to generate the polyvinyl pyridine ruthenium on the surface of electrode, and observe the ECL phenomenon, but electropolymerization method complexity, the condition harshness.N.Egashira etc. have proposed employing Nafion film absorption Ru (bpy) at Chin.J.Chem.17 (1999) 502
3 2+Molecule, but the poor stability of ECL signal.
Summary of the invention: the preparation method who the purpose of this invention is to provide a kind of solid nano gold sol-gel detecting device of electrochemiluminescence;
Another object of the present invention provides a kind of solid nano gold sol-gel of electrochemiluminescence.
With light emitting molecule and organosilane reagent reacting, the hydrolysis of organosilane reagent forms three-dimensional silica colloidal sol, and the effect of silicon ester molecule is the bonding light emitting molecule and constructs the polymer three-dimensional network structure.Silicasol mixes with nano gold sol, and the adding of nm of gold has strengthened electric conductivity and luminous stability, and mixed liquor mixes the surface that drips at electrode and forms luminescent film with polyvinyl alcohol graft copolymerized multipolymer.But the structural stability of polyvinyl alcohol graft copolymerized multipolymer reinforcing membrane, film stick to the surface of electrode and form solid nano gold sol gel electrochemical luminescence detector after solidifying.
It is the electrochemiluminescence molecule that the present invention adopts metal complex, and its structural formula is M (P)
x, wherein M is Ru, and P is a part, and x=3 is the number of part; Part comprises dipyridine, o-phenanthroline, and the carboxylic acid derivates of two pyridines and above part, part can be identical, also can be different.
The silicon ester molecule that the present invention adopts and the molecule ratio of electrochemiluminescence molecule are 1: 1～10
14Between, polyvinyl alcohol graft copolymerized copolymer concentration scope is between 0.1%～50%, and its volume ratio of mixing with sol-gel is 100～1: between 1～100.
Preparation process: take by weighing the terpyridyl ruthenium derivative of 1mmol, add the second eyeball of 20～40mL, add thionyl chloride under argon shield, reflux 1～6 hour obtains the terpyridyl ruthenium derivative of chloride; Decompression distillation is removed the second eyeball and is remained nearly 2～5mL, adds the amino ethyl orthosilicate of 1.1mmol, under the argon shield, reacts 10～24 hours down at 50～70 ℃, obtains the terpyridyl ruthenium derivative of estersilization; Decompression distillation removes and desolvates, product is dissolved in 10～20mL acetone solvent, taking by weighing this product by molecular proportion joins in the aurosol of 10～200nm, the hydrochloric acid that adds methyl silicate and 0.02～0.2M again, ultrasonic 1～6 hour, terpyridyl ruthenium derivative through the hydrolysis estersilization is bonded in the sol-gel, 5～20% polyvinyl alcohol graft copolymerized multipolymers that add 50～200uL again, get the 10uL drips of solution and be added to the surface of glass-carbon electrode, be positioned in the refrigerator 6～24 hours, and obtained solid nano gold sol gel electrochemical luminescence detector.
The present invention is applicable to solid state electrode, and its material can be a metal electrode, as gold, and platinum; Also can be oxide electrode, as the ITO electrode; Can be carbon-based electrode also, as glass-carbon electrode, graphite electrode.
Embodiment is as follows:
Embodiment 1: take by weighing 1.0mmol (4; 4 '-dicarboxyl-2; 2 '-dipyridine) (second bipyridine) ruthenium joins in the cucurbit; the second eyeball that adds 20mL, the thionyl chloride of adding 1.1mmol under argon shield, reflux 6 hours; decompression distillation is removed the second eyeball to nearly 5mL again; the amino ethyl orthosilicate that adds 1.1mmol under the argon shield, reacted 10 hours down at 60 ℃.Decompression distillation removes and desolvates, and product is dissolved in the 20mL acetone solvent, obtains being marked with the amino ethyl orthosilicate of light emitting molecule again through vacuum drying.Get the 0.1mmol product and be dissolved in 500uL particle diameter 5nm aurosol, add the methyl silicate of 10uL, the hydrochloric acid of the 0.02mol/L of 50uL, ultrasonic 1 hour, normal temperature was placed 24 hours down, added the 20% polyvinyl alcohol graft copolymerized multipolymer of 200uL again.Get on the glass-carbon electrode that the 10uL drips of solution is added to diameter 4mm, be positioned in the refrigerator 24 hours, obtain solid nano gold sol gel electrochemical luminescence detector.
The application of solid nano gold sol gel electrochemical luminescence detector
The detection of oxalic acid
Electrode is put into the phosphate solution of the 0.1M that contains 10umol/L oxalic acid, pH=9.5, its galvanochemistry cyclic voltammetry curve and corresponding therewith luminous-potential curve are as shown in Figure 1.Fig. 1 is the electrochemiluminescence cyclic voltammetry curve (A) and corresponding luminous potential curve (B) concentration of oxalic acid: the 10umol/L of oxalic acid, buffer solution: 0.1M phosphate pH=6.8, sweep fast 0.1V/s.Continuous 10 times luminous intensity detects as shown in Figure 2, the ECL signal of continuous 10 detections of the oxalic acid of 10uM, and detecting current potential 1.2V relative standard deviation is 1.8%.What proof solid nano gold sol gel electrode was suitable stablizes.
The working curve that oxalic acid is detected detects the typical curve of oxalic acid, sensing range 2.0-100 umol/L, related coefficient 0.998, lowest detectable limit 1.6umol/L as shown in Figure 3.Proof solid nano gold sol gel electrode is to the detection sensitivity height of oxalic acid, and linear relationship is good.
Embodiment 2: take by weighing 1.0mmol (6-acid amides tetraacethyl-o-phenanthroline) (second bipyridine) ruthenium; join in the cucurbit; add 40mL second eyeball; under argon shield, add the 1.1mmol thionyl chloride; reflux 1 hour, decompression distillation is removed the second eyeball to nearly 2mL again, adds the amino ethyl orthosilicate of 1.1mmol; under the argon shield, reacted 24 hours down at 60 ℃.Decompression distillation removes and desolvates, and product is dissolved in the 10mL acetone solvent, obtains being marked with the amino ethyl orthosilicate of light emitting molecule again through vacuum drying.The product of getting 0.01mmol adds the aurosol of 100uL, particle diameter 5nm, and the methyl silicate of 100uL, the hydrochloric acid of the 0.2mol/L of 5uL, ultrasonic 6 hours, normal temperature was placed 24 hours down, added the 5% polyvinyl alcohol graft copolymerized multipolymer of 50uL again.Get on the platinum electrode that the 10uL drips of solution is added to the 2mm diameter, be positioned in the refrigerator 6 hours, obtain solid nano gold sol gel electrochemical luminescence detector.
The application of solid nano gold sol gel electrochemical luminescence detector
The detection of tripropyl amine (TPA) (TPA)
Electrode is put into the 0.1M phosphate solution that contains 10umol/L TPA, and pH=9.5 applies the detection current potential of 1.3V, and continuous six times ECL intensity as shown in Figure 4.Fig. 4 is the continuous ECL signal that detects for 6 times of 10 TPA, and buffer solution: 0.1M phosphate pH=9.5, as seen from the figure, this detecting device detects TPA has good stability.
Embodiment 3: take by weighing 1.0mmol (6-acid amides tetraacethyl-o-phenanthroline) (two o-phenanthrolines) ruthenium; join in the cucurbit; add 30mL second eyeball; under argon shield, add the 1.1mmol thionyl chloride; reflux 3 hours, decompression distillation is removed the second eyeball to nearly 4mL again, adds the amino ethyl orthosilicate of 1.1mmol; under the argon shield, reacted 12 hours down at 60 ℃.Decompression distillation removes and desolvates, and product is dissolved in the 15mL acetone solvent, obtains being marked with the amino ethyl orthosilicate of light emitting molecule again through vacuum drying.Get the aurosol that this product 0.001mmol adds 100uL particle diameter 5nm, the methyl silicate of 100uL, the hydrochloric acid of the 0.2mol/L of 2uL, ultrasonic 4 hours, normal temperature was placed 16 hours down, added the 15% polyvinyl alcohol graft copolymerized multipolymer of 20uL again.Get on the platinum electrode that the 10uL drips of solution is added to the 2mm diameter, be positioned in the refrigerator 24 hours, obtain solid nano gold sol gel electrochemical luminescence detector.Use this detecting device that the detection sensitivity of proline is reached 1.0 μ mol/L, sensing range 1.0～1000 μ mol/L.
Claims (4)
1. the solid nano gold sol-gel of an electrochemiluminescence, its structural formula is M (P)
x, wherein M is Ru, and P is a part, and x=3 is the number of part; Part comprises dipyridine, the carboxylic acid derivates of o-phenanthroline or these parts, and part can be identical, also can be different.
2. the solid nano gold sol-gel of an electrochemiluminescence is characterized in that part is a dipyridine, o-phenanthroline.
3. the solid nano gold sol-gel of an electrochemiluminescence is characterized in that the carboxylic acid derivates of part is (4,4 '-dicarboxyl-2,2 '-dipyridine) (second bipyridine) ruthenium, (6-acid amides tetraacethyl-o-phenanthroline) (two o-phenanthrolines) ruthenium.
4. the preparation method of an electrochemical luminescence detector for solid nano gold sol-gel, the molecule ratio that it is characterized in that the silicon ester molecule that adopts and electrochemiluminescence molecule is 1: 1～10
14Between, polyvinyl alcohol graft copolymerized copolymer concentration scope is between 0.1%～50%, and its volume ratio of mixing with sol-gel is 100～1: between 1～100;
Preparation process: take by weighing the terpyridyl ruthenium derivative of 1mmol, add the second eyeball of 20～40mL, add thionyl chloride under argon shield, reflux 1～6 hour obtains the terpyridyl ruthenium derivative of chloride; Decompression distillation is removed the second eyeball and is remained nearly 2～5mL, adds the amino ethyl orthosilicate of 1.1mmol, under the argon shield, reacts 10～24 hours down at 50～70 ℃, obtains the terpyridyl ruthenium derivative of estersilization; Decompression distillation removes and desolvates, product is dissolved in 10～20mL acetone solvent, taking by weighing this product by molecular proportion joins in the aurosol of 10～200nm, the hydrochloric acid that adds methyl silicate and 0.02～0.2M again, ultrasonic 1～6 hour, terpyridyl ruthenium derivative through the hydrolysis estersilization is bonded in the sol-gel, 5～20% polyvinyl alcohol graft copolymerized multipolymers that add 50～200uL again, get the 10uL drips of solution and be added to the surface of glass-carbon electrode, be positioned in the refrigerator 6～24 hours, and obtained solid nano gold sol gel electrochemical luminescence detector.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586643A (en) * | 2017-10-30 | 2018-09-28 | 福州大学 | A kind of electrogenerated chemiluminescence hydrogel composite material and the preparation method and application thereof |
| CN113916957A (en) * | 2021-10-29 | 2022-01-11 | 重庆医科大学 | GPBCs/CC and glucose sensor and application thereof |
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2002
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586643A (en) * | 2017-10-30 | 2018-09-28 | 福州大学 | A kind of electrogenerated chemiluminescence hydrogel composite material and the preparation method and application thereof |
| CN113916957A (en) * | 2021-10-29 | 2022-01-11 | 重庆医科大学 | GPBCs/CC and glucose sensor and application thereof |
| CN113916957B (en) * | 2021-10-29 | 2023-06-16 | 重庆医科大学 | GPBCs/CCs, glucose sensor and application thereof |
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