CN105911122A - Method for preparing solid electrochemical luminescence sensor - Google Patents

Method for preparing solid electrochemical luminescence sensor Download PDF

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CN105911122A
CN105911122A CN201610489344.2A CN201610489344A CN105911122A CN 105911122 A CN105911122 A CN 105911122A CN 201610489344 A CN201610489344 A CN 201610489344A CN 105911122 A CN105911122 A CN 105911122A
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pyrene
sensor
kayexalate
pss
functionalization
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CN105911122B (en
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许元红
刘敬权
陈涛
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Qingdao University
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    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/76—Chemiluminescence; Bioluminescence

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Abstract

The invention belongs to the field of photo-initiation reversible addition fragmentation chain transfer (RAFT) polymerization and electrochemical luminescence sensor preparation, and relates to a method for modifying an electrode by using sodium polystyrenesulfonate (PSS) obtained through terpyridyl ruthenium [Ru(bpy)3<2+>] photo-initiation RAT polymerization together with a residual photoinitiator [Ru(bpy)3<2+>], so as to prepare a solid electrochemical luminescence sensor. The method comprises the following steps: preparing PSS by using functionalized cyan-4-ethyl trithioic valeric acid, by using negative charges of PSS and positive charges of a terpyridyl ruthenium initiator, adsorbing [Ru(bpy)3<2+>] by a final polymer product through electrostatic interaction, mixing the prepared PSS with cation exchange resin in a certain ratio, coating the surface of the electrode so as to prepare the solid electrochemical luminescence sensor, or directly soaking an electrode with a surface of a graphene plane into an aqueous solution of PSS for 12-48 hours, through pi-pi overlapping function of a pyrene functional group and the graphene surface, fixing the polymer PSS adsorbed with terpyridyl on the surface of the electrode so as to prepare the solid electrochemical luminescence sensor, and blow-drying with nitrogen.

Description

A kind of preparation method of solid-state electrochemistry illumination sensor
Technical field:
The invention belongs to light-initiated RAFT (RAFT) polymerization and electrochemistry Luminescence sensor preparation field, relates to a kind of method preparing chemical sensor, particularly relates to One utilizes tris (bipyridine) ruthenium [Ru (bpy)3 2+] light-initiated RAFT is polymerized the polystyrene that obtains Sodium sulfonate (PSS) and residual light initiator [Ru (bpy)3 2+] common modified electrode to be to prepare solid-state The method of electrochemical luminous sensor.
Background technology:
At present, due to Photoinitiated reactions mild condition, and can be used for modifying high temperature mutability The biomaterial of protein such as enzyme one class, the most light-initiated increasingly closed by people Note, has been widely used in the fields such as chemical industry.But, owing to, in Photoinitiated reactions, can draw The wave-length coverage of light-emissive polymer is narrow, and light trigger efficiency of initiation is low and light trigger is to environment The problem such as pollution, make their development be restricted.In recent years, tris (bipyridine) ruthenium [Ru(bpy)3 2+] as a kind of novel low-toxicity environment-friendly type light trigger, cause reversible addition fracture chain Transfer (RAFT) polymerization receives the concern of researcher, yet with [Ru (bpy)3 2+] And the suction-operated (such as [Ru (bpy) between polymer3 2+] and electronegative polymer between quiet Electro Sorb effect) make it be difficult to after completion of the reaction remove from polymer, this problem makes This light trigger is never widely used.So Appropriate application [Ru (bpy)3 2+] with poly- Compound adsorbs and is difficult to from polymer remove this point to expanding light-initiated RAFT polymerization tool Significant.
With [Ru (bpy)3 2+] it is that the electrochemiluminescsystem system of probe has easily operation, high detection The advantages such as sensitivity, relatively low signal to noise ratio, this system was subject at analysis detection field in the last few years To paying close attention to widely and studying.Pharmaceutical Analysis, environmental analysis, medical diagnosis on disease etc. can be employed all Multi-field.It addition, based on [Ru (bpy)3 2+] the electrochemical reaction permissible feature of circulation, Ke Yichang By various technology such as layer assembly, Electrostatic Absorption, physically trappings by [Ru (bpy)3 2+] be fixed on Electrode surface sets up solid-state electrochemistry illumination sensor, and the foundation of such sensor has saving examination The features such as agent, simplification device, during setting up this solid-state electrochemistry illumination sensor, can By these new materials such as many Graphenes, CNT and kayexalates (PSS) In order to improve [Ru (bpy) on electrode3 2+] adsorbance, the stability of electrode and electrical conductivity etc., from And improve sensitivity and the Detection results of sensor.Wherein, electronegative polymer P SS can With by with [Ru (bpy)3 2+Electrostatic adsorption between], is effectively improved [Ru (bpy)3 2+] at electricity The adsorbance extremely gone up, increases the stability of prepared electrode.So being a kind of very effective use In preparation [Ru (bpy)3 2+] effective material of solid-state electrochemistry illumination electrode, need to greatly develop also Expansive approach further.Disclosed in the Chinese invention patent of Application No. 201410185102.5 The preparation method of a kind of solid-state electrochemistry illumination sensor, prepares receiving doped with ruthenium complex Meter Jin-silica core shell mould composite construction nano material (Au SiO2-Ru), receive compound Rice material is fixed to the surface of glass-carbon electrode and prepares without reagent electrochemical luminous sensor, although should The electrochemical luminescence reagent of sensor prepared by method is fixed on electrode, can reuse, But this preparation method is strict to preparing ingredient requirement, complicated process of preparation, and preparation process is numerous and diverse, It is difficult to large-scale production.Therefore seek to design the preparation side of a kind of solid-state electrochemistry illumination sensor Method, the method preparation process is simple, and efficiency is high, the good product quality of preparation, building ring Border is friendly, great market prospects.
Summary of the invention:
It is an object of the invention to the shortcoming overcoming prior art to exist, design provide a kind of based on Solid-state electrochemistry prepared by RAFT polymer and residual light initiator that tris (bipyridine) ruthenium is light-initiated The method of luminescence sensor, Appropriate application [Ru (bpy)3 2+] cause RAFT knot as light trigger Conjunction obtains polymer P SS, forms stable compound by electrostatic adsorption with PSS, auxiliary Help with ion exchange and π-π superposition mode, set up stability and high efficiency ground solid-state electrochemistry and send out Optical sensor.
To achieve these goals, the present invention relates to prepares solid-state electrochemistry illumination sensor Concrete technology comprises the following steps:
1, tris (bipyridine) ruthenium is utilized to cause RAFT polymerization to prepare polymer as light trigger PSS:
(1) by 47-60mg RAFT reagent (4-cyano group-4-ethyl trithio is for valeric acid, CETP), Monomer (sodium p styrene sulfonate, SSS) electronegative under 2-6g pH neutrallty condition and 1-10 Mg tris (bipyridine) ruthenium uses 3-6mL water and 4-8mL dioxane in the volumetric flask of 50mL Carry out dissolving to obtain reagent；
(2) step (1) will remove oxygen equipped with being passed through nitrogen 20-40 minute in the volumetric flask of reagent Gas；
(3) volumetric flask after deoxygenation in step (2) is irradiated under the blue-ray light of 150-200W 12-48h；
(4) step (3) products therefrom is dialysed 2-4 days in ultra-pure water, be then placed in vacuum tank In be dried, obtain polymer P SS；
(5) PSS by the RAFT tube-nursery of non-for above-mentioned employing pyrene functionalization is named PSS1；
2, RAFT reagent (4-cyano group-4-ethyl trithio is for valeric acid, CETP) is carried out sense Changing, the group for functionalization includes pyrene, hydroxyl, amino, carboxyl, sulfydryl, nitro, sulphur Acidic group and acid chloride group etc., according to the PSS of the different different functionalizations of demand synthesis, select RAFT Reagent carries out pyrene functionalization, and concrete technology comprises the following steps:
(1) 0.5-2g pyrene methyl alcohol, 0.73-3g CETP, 0.6383-1g bis-are taken respectively Carbodicyclo hexylimide (DCC) and 0.0378-0.06g DMAP (DMAP) Be dissolved in 8-20mL oxolane (THF) mixture standby；
(2) step (1) gained mixture is stirred at room temperature reaction 12-36h, then Solids removed by filtration accessory substance obtains filtrate；
(3) according to ethyl acetate and n-hexane after the filtrate rotation steaming that will obtain from step (2) The part by weight of 30:70 crosses silicagel column, and the product obtained is the CETP of pyrene functionalization (PCETP)；
3, use the RAFT reagent of pyrene functionalization by light initiation polymerization synthesis pyrene functionalization PSS process, concrete technology comprises the following steps:
(1) by 20-66mg RAFT reagent (CETP of pyrene functionalization, PCETP), 2-6g pH Monomer (sodium p styrene sulfonate, SSS) electronegative under neutrallty condition, 1-10mg tri- Pyridine ruthenium dissolves with 3-6mL water and 4-8mL dioxane in the volumetric flask of 50mL；
(2) step (1) will remove oxygen equipped with being passed through nitrogen 20-40 minute in the volumetric flask of reagent Gas；
(3) volumetric flask after deoxygenation in step (2) is irradiated also under the blue-ray light of 150-200W Stirring reaction 12-48h；
(4) step (3) products therefrom is dialysed 2-4 days in ultra-pure water, be then placed in vacuum tank In be dried, obtain polymer P SS；
(5) by the named PSS2 of PSS of the RAFT tube-nursery of above-mentioned employing pyrene functionalization；
4, the preparation of solid-state electrochemistry illumination sensor:
Utilize negative electrical charge and the positive charge of tris (bipyridine) ruthenium initiator band that polymer P SS carries, Make to adsorb [Ru (bpy) by electrostatic interaction on polymer end product3 2+], it is difficult to by washing Step removes the [Ru (bpy) of absorption3 2+], it is not necessary to add electrochemical luminescence probe again, it becomes possible to will In the polymer P SS1 synthesized in step 1 and step 3, the polymer P SS2 of synthesis is for electricity The structure of chemiluminescence sensor, use the exchange of Electrostatic Absorption, ion, physically trapping or π- One or more methods in π superposition, by step 1 synthesis PSS1 in water molten Solve and prepare concentration more than the 0.1mM PSS1 aqueous solution, the prepared PSS1 aqueous solution and cation Exchanger resin (such as Nafion) mixes according to volume ratio 20:1-1:20 ratio, more directly drop coating Solid-state electrochemistry illumination sensor is i.e. obtained to electrode surface infrared drying 10-60s；Or by table Face is in the aqueous solution of the PSS2 that the electrode of graphene planes is immersed directly in 5-20mM 12-48h, by the π-π superposition of pyrene functional group Yu graphenic surface, will be adsorbed with The polymer P SS2 of terpyridyl is fixed to electrode surface, constitutes solid-state electrochemistry illumination sensing Device, more obtained sensor nitrogen is dried up, in order to test；
5, sensor carries out reappear performance detect:
Testing the reappearance of prepared sensor, after scanning 3000s, fluorescence is strong continuously Degree fall is less than 1%, and the sensor of preparation reappears functional, stable performance；To institute After the long-time stability of the sensor of preparation are measured 90 days, its electrochemical luminescence intensity drops Low less than 10%, show that prepared electrochemical luminous sensor long-time stability are good.
Compared with prior art, its preparation process is simple for the present invention, and preparation efficiency is high, produces Quality is good, and stability is strong, and applied environment is friendly.
Accompanying drawing illustrates:
Fig. 1 is the building-up process principle schematic of the polymer P SS that the present invention relates to.
Fig. 2 A is the electrochemical luminescence that the electrochemical luminous sensor prepared scans 3000s continuously Intensity map；Fig. 2 B is the test figure of the electrochemical luminous sensor long-time stability of preparation.
Detailed description of the invention:
Below by embodiment and combine accompanying drawing the invention will be further described.
1, polymer is prepared in the RAFT polymerization utilizing tris (bipyridine) ruthenium to cause as light trigger PSS:
(1) by 60mg RAFT reagent (4-cyano group-4-ethyl trithio is for valeric acid, CETP), 6 G sodium p styrene sulfonate and 10mg tris (bipyridine) ruthenium use 6mL in the volumetric flask of 50mL Water and 8mL dioxane dissolve reagent is standby；
(2) step (1) will remove oxygen equipped with being passed through nitrogen 40 minutes in the volumetric flask of reagent；
(3) volumetric flask after deoxygenation in step (2) is irradiated 48h under the blue-ray light of 200W；
(4) step (3) products therefrom is dialysed 4 days in ultra-pure water, be then placed in vacuum tank It is dried, obtains polymer P SS；
(5) PSS by the RAFT tube-nursery of non-for above-mentioned employing pyrene functionalization is named PSS1；
Embodiment 2:
4-cyano group-4-ethyl trithio is carried out pyrene functionalization for valeric acid (CETP) by the present embodiment, 4-cyano group-4-ethyl the trithio of the pyrene functionalization obtaining pyrene functionalization is tried for valeric acid (PCETP) Agent, specifically comprises the processes of:
(1) 0.5g pyrene methyl alcohol, 0.73g CETP, 0.6383g dicyclohexyl carbon are taken respectively Diimine (DCC) and 0.0378g DMAP (DMAP) are dissolved in 10mL tetra- Hydrogen furans (THF) obtains mixture；
(2) step (1) described mixture is stirred at room temperature reaction 12h, then filters Remove solid by-product and obtain filtrate；
(3) according to ethyl acetate and n-hexane after the filtrate rotation steaming that will obtain from step (2) The part by weight of 30:70 crosses silicagel column, the product obtained i.e. PCETP；
Embodiment 3:
The RAFT reagent using pyrene functionalization illustrates to synthesize pyrene official's energy by light initiation polymerization The PSS process changed, concrete technology comprises the following steps:
(1) by the 23.9mg RAFT reagent (4-cyano group-4-ethyl trithio generation penta of pyrene functionalization Acid, PCETP), electronegative under 2.06g pH neutrallty condition monomer (p styrene sulfonic acid Sodium) and 1.5mg tris (bipyridine) ruthenium use 3.5mL water and 3.5mL in the volumetric flask of 50mL Dioxane carries out dissolving to obtain reagent；
(2) step (1) will remove oxygen equipped with being passed through nitrogen 30 minutes in the volumetric flask of reagent；
(3) volumetric flask after deoxygenation in step (2) is irradiated under the blue-ray light of 165W and stirs Reaction 24h；
(4) step (3) products therefrom is dialysed 3 days in ultra-pure water, be then placed in vacuum tank It is dried, obtains polymer P SS；
(5) by the named PSS2 of PSS of the RAFT tube-nursery of above-mentioned employing pyrene functionalization；
Embodiment 4:
It is the 5mM PSS1 aqueous solution that PSS1 dissolves prepared concentration in water, prepared PSS1 The aqueous solution mixes according to volume ratio 1:1 ratio with cationic ion-exchange resin (such as Nafion), Directly drop coating i.e. obtains solid-state electrochemistry illumination sensor to electrode surface infrared drying 60s again；
Embodiment 5:
In the aqueous solution of the PSS2 that high temperature pyrolysis graphite electrode is immersed directly in 10mM 24 H, by the π-π superposition of pyrene functional group Yu graphenic surface, will be adsorbed with three pyrroles The polymer P SS2 of pyridine is fixed to electrode surface, prepares solid-state electrochemistry illumination sensor, then Obtained sensor nitrogen is dried up and i.e. obtains solid-state electrochemistry illumination sensor；
Embodiment 6:
Solid-state electrochemical sensor reappearance and the long-time stability of preparation are carried out by the present embodiment Test:
The reappearance of prepared solid-state electrochemical sensor is tested, as shown in Figure 2 A, After scanning 3000s, fluorescence intensity fall is less than 1% continuously, and the solid-state electrochemistry of preparation passes Sensor reappears functional, stable performance；Long-term to prepared solid-state electrochemical sensor After stability is measured 90 days, its electrochemical luminescence intensity reduces less than 10%, preparation Solid-state electrochemical sensor long-time stability good.

Claims (2)

1. the preparation method of a solid-state electrochemistry illumination sensor, it is characterised in that concrete technology comprises the following steps:
(1) tris (bipyridine) ruthenium is utilized to cause RAFT polymerization to prepare polymers polystyrene sodium sulfonate as light trigger:
(1) carry out dissolving to obtain reagent with 3-6mL water and 4-8mL dioxane for electronegative sodium p styrene sulfonate and 1-10mg tris (bipyridine) ruthenium under valeric acid, 2-6g pH neutrallty condition in the volumetric flask of 50mL by 47-60mg RAFT reagent 4-cyano group-4-ethyl trithio；
(2) step (1) will remove oxygen equipped with being passed through nitrogen 20-40 minute in the volumetric flask of reagent；
(3) volumetric flask after deoxygenation in step (2) is irradiated 12-48h under the blue-ray light of 150-200W；
(4) step (3) products therefrom is dialysed 2-4 days in ultra-pure water, be then placed in vacuum tank being dried, obtain polymers polystyrene sodium sulfonate；
(5) by the named kayexalate of kayexalate 1 of the RAFT tube-nursery of non-for above-mentioned employing pyrene functionalization；
(2) for valeric acid, RAFT reagent 4-cyano group-4-ethyl trithio being carried out pyrene functionalization, concrete technology comprises the following steps:
(1) take 0.5-2g pyrene methyl alcohol, 0.73-3g CETP, 0.6383-1g dicyclohexylcarbodiimide and 0.0378-0.06g DMAP respectively to be dissolved in 8-20mL oxolane to prepare mixture standby；
(2) step (1) gained mixture is stirred at room temperature reaction 12-36h, and then solids removed by filtration accessory substance obtains filtrate；
(3) crossing silicagel column according to the part by weight of ethyl acetate and n-hexane 30:70 after the filtrate obtained from step (2) rotation being steamed, the product obtained is the 4-cyano group-4-ethyl trithio of pyrene functionalization for valeric acid；
(3) using the RAFT reagent kayexalate process by light initiation polymerization synthesis pyrene functionalization of pyrene functionalization, concrete technology comprises the following steps:
(1) the 4-cyano group-4-ethyl trithio of 20-66mg pyrene functionalization is dissolved with 3-6mL water and 4-8mL dioxane in the volumetric flask of 50mL for valeric acid, sodium p styrene sulfonate electronegative under 2-6g pH neutrallty condition, 1-10mg tris (bipyridine) ruthenium；
(2) step (1) will remove oxygen equipped with being passed through nitrogen 20-40 minute in the volumetric flask of reagent；
(3) volumetric flask after deoxygenation in step (2) irradiated under the blue-ray light of 150-200W and stir reaction 12-48h；
(4) step (3) products therefrom is dialysed 2-4 days in ultra-pure water, be then placed in vacuum tank being dried, obtain polymers polystyrene sodium sulfonate；
(5) by the named kayexalate of kayexalate 2 of the RAFT tube-nursery of above-mentioned employing pyrene functionalization；
(4) preparation of solid-state electrochemistry illumination sensor:
Utilize negative electrical charge and the positive charge of tris (bipyridine) ruthenium initiator band of polymers polystyrene sodium sulfonate band, make to adsorb [Ru (bpy) by electrostatic interaction on polymer end product3 2+], it is difficult to the step by washing and removes [the Ru (bpy) of absorption3 2+], without adding electrochemical luminescence probe again, just the polymers polystyrene sodium sulfonate 2 of synthesis in the polymers polystyrene sodium sulfonate 1 synthesized in step 1 and step 3 can be used for the structure of electrochemical luminous sensor, use Electrostatic Absorption, ion exchanges, one or more methods in physically trapping or π-π superposition, the kayexalate 1 of synthesis in step 1 is dissolved in water and prepares concentration more than 0.1mM kayexalate 1 aqueous solution, kayexalate 1 aqueous solution prepared mixes according to volume ratio 20:1-1:20 ratio with cationic ion-exchange resin, directly drop coating i.e. obtains solid-state electrochemistry illumination sensor to electrode surface infrared drying 10-60s again；Or 12-48h in the aqueous solution of the kayexalate 2 that the electrode that surface is graphene planes is immersed directly in 5-20mM, π-π superposition by pyrene functional group Yu graphenic surface, the polymers polystyrene sodium sulfonate 2 being adsorbed with terpyridyl is fixed to electrode surface, constitute solid-state electrochemistry illumination sensor, again obtained sensor nitrogen is dried up, in order to test.
The preparation method of solid-state electrochemistry illumination sensor the most according to claim 1, it is characterized in that the reappearance of prepared sensor is tested, after scanning 3000s, fluorescence intensity fall is less than 1% continuously, and the sensor of preparation reappears functional, stable performance；After long-time stability to prepared sensor are measured 90 days again, its electrochemical luminescence intensity reduces less than 10%, and the electrochemical luminous sensor long-time stability of preparation are good.
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CN108918483A (en) * 2018-05-08 2018-11-30 青岛大学 A kind of photocatalysis RAFT polymerization prepares the method and its application of molecular engram sensor
CN110308142A (en) * 2019-07-25 2019-10-08 常州大学 A kind of tetracycline flexibility class goldleaf electrochemical luminescence sensor and preparation method thereof and detection method
CN113155916A (en) * 2021-02-08 2021-07-23 中国科学院长春应用化学研究所 Solid-state electrochemical luminescence probe and preparation method thereof
CN114994132A (en) * 2022-08-01 2022-09-02 成都工业学院 Method for testing regulation and control of Rh-N4-graphene hydrogen evolution performance by stress

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108918483A (en) * 2018-05-08 2018-11-30 青岛大学 A kind of photocatalysis RAFT polymerization prepares the method and its application of molecular engram sensor
CN110308142A (en) * 2019-07-25 2019-10-08 常州大学 A kind of tetracycline flexibility class goldleaf electrochemical luminescence sensor and preparation method thereof and detection method
CN110308142B (en) * 2019-07-25 2021-07-27 常州大学 Tetracycline flexible gold-like foil electrochemical luminescence sensor and preparation method and detection method thereof
CN113155916A (en) * 2021-02-08 2021-07-23 中国科学院长春应用化学研究所 Solid-state electrochemical luminescence probe and preparation method thereof
CN113155916B (en) * 2021-02-08 2024-02-13 中国科学院长春应用化学研究所 Solid-state electrochemiluminescence probe and preparation method thereof
CN114994132A (en) * 2022-08-01 2022-09-02 成都工业学院 Method for testing regulation and control of Rh-N4-graphene hydrogen evolution performance by stress

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