CN105911122B - A kind of preparation method of solid-state electrochemistry illumination sensor - Google Patents

A kind of preparation method of solid-state electrochemistry illumination sensor Download PDF

Info

Publication number
CN105911122B
CN105911122B CN201610489344.2A CN201610489344A CN105911122B CN 105911122 B CN105911122 B CN 105911122B CN 201610489344 A CN201610489344 A CN 201610489344A CN 105911122 B CN105911122 B CN 105911122B
Authority
CN
China
Prior art keywords
solid
pyrene
sensor
raft
functionalization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610489344.2A
Other languages
Chinese (zh)
Other versions
CN105911122A (en
Inventor
许元红
刘敬权
陈涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao University
Original Assignee
Qingdao University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao University filed Critical Qingdao University
Priority to CN201610489344.2A priority Critical patent/CN105911122B/en
Publication of CN105911122A publication Critical patent/CN105911122A/en
Application granted granted Critical
Publication of CN105911122B publication Critical patent/CN105911122B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Plasma & Fusion (AREA)
  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • Electrochemistry (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention belongs to light-initiated RAFT (RAFT) polymerization and electrochemical luminescence sensor preparation field, is related to one kind and utilizes tris (bipyridine) ruthenium [Ru (bpy)3 2+] light-initiated RAFT polymerize obtained kayexalate (PSS) and residual light trigger [Ru (bpy)3 2+] common modified electrode to be to prepare the method for solid-state electrochemistry illumination sensor, PSS is prepared by 4 ethyl of cyano group, the three thio valeric acid of functionalization, using the negative electrical charge of PSS bands and the positive charge of tris (bipyridine) ruthenium initiator band, make to adsorb [Ru (bpy) by electrostatic interaction on polymer final product3 2+], obtained PSS is mixed with cationic ion-exchange resin certain proportion, electrode surface is coated onto solid-state electrochemistry illumination sensor is made, or surface is immersed directly in 12 48h in the PSS aqueous solution for the electrode of graphene planes, pass through the π π superpositions of pyrene functional group and graphenic surface, the polymer P SS for being adsorbed with terpyridyl is fixed to electrode surface, solid-state electrochemistry illumination sensor is made, is dried up 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 electrochemical luminescence sensor to prepare neck Domain, it is related to a kind of method for preparing chemical sensor, tris (bipyridine) ruthenium [Ru (bpy) is utilized more particularly to one kind3 2+] light-initiated RAFT polymerize obtained kayexalate (PSS) and residual light trigger [Ru (bpy)3 2+] common modified electrode to be to prepare The method of solid-state electrochemistry illumination sensor.
Background technology：
At present, due to Photoinitiated reactions mild condition, and it can be used for modifying the protein such as enzyme of high temperature mutability A kind of biomaterial, thus it is light-initiated have been to be concerned by more and more people, be widely used in the fields such as chemical industry.However, Due to the wave-length coverage of photopolymerization in Photoinitiated reactions, can be triggered narrow, light trigger efficiency of initiation is low and light trigger The problems such as pollution to environment, it is restricted their development.In recent years, tris (bipyridine) ruthenium [Ru (bpy)3 2+] it is used as one Kind novel low-toxicity environment-friendly type light trigger, RAFT (RAFT) polymerization is triggered to receive the pass of researcher Note, yet with [Ru (bpy)3 2+] suction-operated (such as [Ru (bpy) between polymer3 2+] with negatively charged polymer it Between electrostatic adsorption) cause its be difficult to be removed from polymer after completion of the reaction, this problem makes the light trigger one It is not widely used directly.So rationally utilize [Ru (bpy)3 2+] be not easy to remove from polymer with Polymer adsorption This point is significant to expanding light-initiated RAFT polymerizations.
With [Ru (bpy)3 2+] for the electrochemiluminescsystem system of probe there is easy to operate, high detection sensitivity, relatively low The advantages that signal to noise ratio, this system were widely paid close attention to and studied in analysis detection field in the last few years.Medicine can be employed The numerous areas such as analysis, environmental analysis, medical diagnosis on disease.In addition, it is based on [Ru (bpy)3 2+] electrochemical reaction circulation can with spy Point, can be usually through the various technologies such as layer assembly, Electrostatic Absorption, physically trapping by [Ru (bpy)3 2+] it is fixed on electrode surface Solid-state electrochemistry illumination sensor is established, the foundation of such sensor has the characteristics that to save reagent, simplifies device, should establishing , can be by many graphenes, CNT and kayexalate (PSS) etc. during solid-state electrochemistry illumination sensor These new materials are improving on electrode [Ru (bpy)3 2+] adsorbance, the stability of electrode and electrical conductivity etc., passed so as to improve The sensitivity of sensor and Detection results.Wherein, electronegative polymer P SS can by with [Ru (bpy)3 2+] between electrostatic Suction-operated, effectively improve [Ru (bpy)3 2+] adsorbance on electrode, the stability of electrode prepared by increase.So it is one Kind is very effective to be used to prepare [Ru (bpy)3 2+] effective material of solid-state electrochemistry illumination electrode goes forward side by side, it is necessary to greatly develop One step expands application.A kind of solid-state electrochemistry illumination is disclosed in the Chinese invention patent of Application No. 201410185102.5 to pass The preparation method of sensor, prepare the nanogold doped with ruthenium complex-silica core shell mould composite construction nano material (Au SiO2- Ru), the surface that composite nano materials are fixed to glass-carbon electrode is made without reagent electrochemical luminescence sensor, although should The electrochemical luminescence reagent of sensor prepared by method is fixed on electrode, may be reused, but the preparation method is to system Standby ingredient requirement is strict, and preparation technology is complicated, and preparation process is numerous and diverse, it is difficult to large-scale production.Therefore seek to design a kind of solid-state The preparation method of electrochemical luminescence sensor, this method preparation process is simple, efficiency high, the good product quality of preparation, work Make environment-friendly, great market prospects.
The content of the invention：
The shortcomings that it is an object of the invention to overcome prior art to exist, design are provided one kind and drawn based on tris (bipyridine) ruthenium light The method that the RAFT polymer and residual light trigger of hair prepare solid-state electrochemistry illumination sensor, rationally utilizes [Ru (bpy)3 2+] be used as light trigger to trigger RAFT combinations to obtain polymer P SS, stabilization is formed by electrostatic adsorption and PSS Compound, aid in a manner of ion exchange and π-π superpositions, with establishing stability and high efficiency solid-state electrochemistry illumination sensor.
To achieve these goals, the concrete technology of the present invention for preparing solid-state electrochemistry illumination sensor include with Lower step：
1st, RAFT polymerizations are triggered to prepare polymer P SS by the use of tris (bipyridine) ruthenium as light trigger：
(1) by under 47-60mg RAFT reagents (three thio valeric acid of 4- cyano group -4- ethyls, CETP), 2-6g pH neutrallty conditions Negatively charged monomer (sodium p styrene sulfonate, SSS) and 1-10mg tris (bipyridine) rutheniums use 3-6mL water in 50mL volumetric flask Carry out dissolving to obtain reagent with 4-8mL dioxane；
(2) nitrogen 20-40 minutes will be passed through in the volumetric flask equipped with reagent in step (1) and removes oxygen；
(3) volumetric flask after deoxygenation in step (2) is irradiated into 12-48h under 150-200W blue-ray light；
(4) step (3) products therefrom is dialysed 2-4 days in ultra-pure water, is then placed in vacuum tank and dries, polymerize Thing PSS；
(5) PSS of the above-mentioned RAFT tube- nurseries using non-pyrene functionalization is named as PSS1；
2nd, RAFT reagents (three thio valeric acid of 4- cyano group -4- ethyls, CETP) are functionalized, the group for functionalization Including pyrene, hydroxyl, amino, carboxyl, sulfydryl, nitro, sulfonic group and acid chloride group etc., different functionalizations are synthesized according to different demands PSS, select RAFT reagents carrying out pyrene functionalization, concrete technology comprises the following steps：
(1) take respectively 0.5-2g pyrenes methanol, 0.73-3g CETP, 0.6383-1g dicyclohexylcarbodiimides (DCC) and 0.0378-0.06g DMAPs (DMAP) be dissolved in 8-20mL tetrahydrofurans (THF) mixture it is standby；
(2) reaction 12-36h is stirred at room temperature in mixture obtained by step (1), is then filtered to remove solid by-product and obtains Filtrate；
(3) according to ethyl acetate and n-hexane 30 after the filtrate revolving that will be obtained from step (2):70 part by weight mistake Silicagel column, obtained product are the CETP (PCETP) of pyrene functionalization；
3rd, the PSS processes of pyrene functionalization, concrete technology are synthesized by light initiation polymerization using the RAFT reagents of pyrene functionalization Comprise the following steps：
(1) it is negatively charged under 2-6g pH neutrallty conditions by 20-66mg RAFT reagents (CETP of pyrene functionalization, PCETP) Monomer (sodium p styrene sulfonate, SSS), 1-10mg tris (bipyridine) rutheniums use 3-6mL water and 4-8mL bis- in 50mL volumetric flask The ring of oxygen six dissolves；
(2) nitrogen 20-40 minutes will be passed through in the volumetric flask equipped with reagent in step (1) and removes oxygen；
(3) volumetric flask after deoxygenation in step (2) is irradiated to simultaneously stirring reaction 12-48h under 150-200W blue-ray light；
(4) step (3) products therefrom is dialysed 2-4 days in ultra-pure water, is then placed in vacuum tank and dries, polymerize Thing PSS；
(5) PSS of the above-mentioned RAFT tube- nurseries using pyrene functionalization is named as PSS2；
4th, the preparation of solid-state electrochemistry illumination sensor：
Using the negative electrical charge of polymer P SS bands and the positive charge of tris (bipyridine) ruthenium initiator band, make polymer final product It is upper that [Ru (bpy) is adsorbed by electrostatic interaction3 2+], it is difficult to which the step of passing through washing removes the [Ru (bpy) of absorption3 2+], without again Add electrochemical luminescence probe, it becomes possible to use the polymer P SS2 synthesized in the polymer P SS1 and step 3 that are synthesized in step 1 In the structure of electrochemical luminescence sensor, one kind or one in being superimposed using Electrostatic Absorption, ion exchange, physically trapping or π-π Kind above method, the PSS1 synthesized in step 1 is dissolved into obtained concentration in water and is more than the 0.1mM PSS1 aqueous solution, it is obtained The PSS1 aqueous solution is with cationic ion-exchange resin (such as Nafion) according to volume ratio 20:1-1:20 ratios mix, then direct drop coating arrives Electrode surface infrared drying 10-60s obtains solid-state electrochemistry illumination sensor；It is or surface is straight for the electrode of graphene planes 12-48h in the aqueous solution for the PSS2 for being immersed in 5-20mM is met, by the π-π superpositions of pyrene functional group and graphenic surface, The polymer P SS2 for being adsorbed with terpyridyl is fixed to electrode surface, forms solid-state electrochemistry illumination sensor, then will be made Obtain sensor to be dried up with nitrogen, to test；
5th, reproduction performance detection is carried out to sensor：
The reappearance of prepared sensor is tested, continuous fluorescence intensity fall deficiency after scanning 3000s 1%, the sensor of preparation reappears functional, stable performance；90 are measured to the long-time stability of prepared sensor After it, its electrochemical luminescence intensity decreases is less than 10%, shows that prepared electrochemical luminescence sensor long-time stability are good It is good.
Compared with prior art, its preparation process is simple by the present invention, and preparation efficiency is high, good product quality, stability Can be strong, application environment is friendly.
Brief description of the drawings：
Fig. 1 is polymer P SS of the present invention building-up process principle schematic.
Fig. 2A is the electrochemical luminescence intensity map that the electrochemical luminescence sensor prepared continuously scans 3000s；Fig. 2 B are system The test chart of standby electrochemical luminescence sensor long-time stability.
Embodiment：
The invention will be further described by way of example and in conjunction with the accompanying drawings.
1st, the RAFT polymerizations triggered by the use of tris (bipyridine) ruthenium as light trigger prepare polymer P SS：
(1) by 60mg RAFT reagents (three thio valeric acid of 4- cyano group -4- ethyls, CETP), 6g sodium p styrene sulfonates and 10mg tris (bipyridine) rutheniums in 50mL volumetric flask with 6mL water and 8mL dioxane dissolve reagent is standby；
(2) it will be equipped with step (1) in the volumetric flask of reagent and be passed through 40 minutes removing oxygen of nitrogen；
(3) volumetric flask after deoxygenation in step (2) is irradiated into 48h under 200W blue-ray light；
(4) step (3) products therefrom is dialysed 4 days in ultra-pure water, is then placed in vacuum tank and dries, obtain polymer PSS；
(5) PSS of the above-mentioned RAFT tube- nurseries using non-pyrene functionalization is named as PSS1；
Embodiment 2：
Three thio valeric acid (CETP) of 4- cyano group -4- ethyls is carried out pyrene functionalization by the present embodiment, obtains the pyrene of pyrene functionalization Thio valeric acid (PCETP) reagent of 4- cyano group -4- ethyls three of functionalization, concrete technology are：
(1) 0.5g pyrenes methanol, 0.73g CETP, 0.6383g dicyclohexylcarbodiimides (DCC) and 0.0378g are taken respectively DMAP (DMAP) is dissolved in 10mL tetrahydrofurans (THF) and obtains mixture；
(2) reaction 12h is stirred at room temperature in step (1) described mixture, being then filtered to remove solid by-product must filter Liquid；
(3) according to ethyl acetate and n-hexane 30 after the filtrate revolving that will be obtained from step (2):70 part by weight mistake Silicagel column, obtained product i.e. PCETP；
Embodiment 3：
The PSS processes that pyrene functionalization is synthesized by light initiation polymerization are illustrated using the RAFT reagents of pyrene functionalization, specifically Technique comprises the following steps：
(1) by 23.9mg RAFT reagents (the three thio valeric acid of 4- cyano group -4- ethyls of pyrene functionalization, PCETP), 2.06g Negatively charged monomer (sodium p styrene sulfonate) and 1.5mg tris (bipyridine) rutheniums are used in 50mL volumetric flask under pH neutrallty conditions 3.5mL water and 3.5mL dioxane carry out dissolving to obtain reagent；
(2) it will be equipped with step (1) in the volumetric flask of reagent and be passed through 30 minutes removing oxygen of nitrogen；
(3) volumetric flask after deoxygenation in step (2) is irradiated to simultaneously stirring reaction 24h under 165W blue-ray light；
(4) step (3) products therefrom is dialysed 3 days in ultra-pure water, is then placed in vacuum tank and dries, obtain polymer PSS；
(5) PSS of the above-mentioned RAFT tube- nurseries using pyrene functionalization is named as PSS2；
Embodiment 4：
PSS1 dissolves that concentration is made is the 5mM PSS1 aqueous solution in water, obtained the PSS1 aqueous solution and cation exchange tree Fat (such as Nafion) is according to volume ratio 1：1 ratio mixes, then direct drop coating obtains solid-state electricity to electrode surface infrared drying 60s Chemiluminescence sensor；
Embodiment 5：
High temperature pyrolysis graphite electrode is immersed directly in 24h in the 10mM PSS2 aqueous solution, by pyrene functional group with π-π the superpositions of graphenic surface, the polymer P SS2 for being adsorbed with terpyridyl is fixed to electrode surface, prepares solid-state electricity Chemiluminescence sensor, then obtained sensor nitrogen drying is obtained into solid-state electrochemistry illumination sensor；
Embodiment 6：
The present embodiment is tested the solid-state electrochemical sensor reappearance and long-time stability of preparation：
The reappearance of prepared solid-state electrochemical sensor is tested, as shown in Figure 2 A, after continuous scanning 3000s For fluorescence intensity fall less than 1%, the solid-state electrochemical sensor of preparation reappears functional, stable performance；To prepared Solid-state electrochemical sensor long-time stability be measured 90 days after, its electrochemical luminescence intensity decreases is less than 10%, The solid-state electrochemical sensor long-time stability of preparation are good.

Claims (2)

1. a kind of preparation method of solid-state electrochemistry illumination sensor, it is characterised in that concrete technology comprises the following steps：
(1) RAFT polymerizations are triggered to prepare polymers polystyrene sodium sulfonate by the use of tris (bipyridine) ruthenium as light trigger：
(1) will be negatively charged under three thio valeric acid of 47-60mg RAFT reagent 4- cyano group -4- ethyls, 2-6g pH neutrallty conditions Sodium p styrene sulfonate and 1-10mg tris (bipyridine) rutheniums are carried out in 50mL volumetric flask with 3-6mL water and 4-8mL dioxane Dissolve to obtain reagent；
(2) nitrogen 20-40 minutes will be passed through in the volumetric flask equipped with reagent in step (1) and removes oxygen；
(3) volumetric flask after deoxygenation in step (2) is irradiated into 12-48h under 150-200W blue-ray light；
(4) step (3) products therefrom is dialysed 2-4 days in ultra-pure water, is then placed in vacuum tank and dries, obtain polymer poly SSS；
(5) kayexalate of the above-mentioned RAFT tube- nurseries using non-pyrene functionalization is named as kayexalate 1；
(2) pyrene functionalization is carried out to three thio valeric acid of RAFT reagent 4- cyano group -4- ethyls, concrete technology comprises the following steps：
(1) 0.5-2g pyrenes methanol, 0.73-3g CETP, 0.6383-1g dicyclohexylcarbodiimides and 0.0378- are taken respectively It is standby that 0.06g DMAPs are dissolved in the obtained mixture of 8-20mL tetrahydrofurans；
(2) reaction 12-36h is stirred at room temperature in mixture obtained by step (1), being then filtered to remove solid by-product must filter Liquid；
(3) according to ethyl acetate and n-hexane 30 after the filtrate revolving that will be obtained from step (2):70 part by weight crosses silica gel Post, obtained product are the three thio valeric acid of 4- cyano group -4- ethyls of pyrene functionalization；
(3) the kayexalate process of pyrene functionalization is synthesized by light initiation polymerization using the RAFT reagents of pyrene functionalization, Concrete technology comprises the following steps：
(1) it is negatively charged under 2-6g pH neutrallty conditions by the three thio valeric acid of 4- cyano group -4- ethyls of 20-66mg pyrene functionalizations Sodium p styrene sulfonate, 1-10mg tris (bipyridine) rutheniums are dissolved in 50mL volumetric flask with 3-6mL water and 4-8mL dioxane；
(2) nitrogen 20-40 minutes will be passed through in the volumetric flask equipped with reagent in step (1) and removes oxygen；
(3) volumetric flask after deoxygenation in step (2) is irradiated to simultaneously stirring reaction 12-48h under 150-200W blue-ray light；
(4) step (3) products therefrom is dialysed 2-4 days in ultra-pure water, is then placed in vacuum tank and dries, obtain polymer poly SSS；
(5) kayexalate of the above-mentioned RAFT tube- nurseries using pyrene functionalization is named as kayexalate 2；
(4) preparation of solid-state electrochemistry illumination sensor：
Using the negative electrical charge of polymers polystyrene sodium sulfonate band and the positive charge of tris (bipyridine) ruthenium initiator band, make polymer most [Ru (bpy) is adsorbed by electrostatic interaction on end-product3 2+], it is difficult to which the step of passing through washing removes the [Ru (bpy) of absorption3 2+], Without adding electrochemical luminescence probe again, it becomes possible to by the polymers polystyrene sodium sulfonate 1 and step 3 that are synthesized in step 1 The polymers polystyrene sodium sulfonate 2 of synthesis be used for electrochemical luminescence sensor structure, using Electrostatic Absorption, ion exchange, One or more kinds of methods in physically trapping or π-π superpositions, by the kayexalate 1 synthesized in step 1 in water Dissolving is made concentration and is more than the aqueous solution of 0.1mM kayexalates 1, the obtained aqueous solution of kayexalate 1 with it is positive from Sub-exchange resin is according to volume ratio 20:1-1:20 ratios mix, then direct drop coating produces to electrode surface infrared drying 10-60s To solid-state electrochemistry illumination sensor；Or surface is immersed directly in 5-20mM polystyrene sulphur for the electrode of graphene planes 12-48h in the aqueous solution of sour sodium 2, by the π-π superpositions of pyrene functional group and graphenic surface, three pyrroles will be adsorbed with The polymers polystyrene sodium sulfonate 2 of pyridine is fixed to electrode surface, forms solid-state electrochemistry illumination sensor, then by obtained biography Sensor is dried up with nitrogen, to test.
2. the preparation method of solid-state electrochemistry illumination sensor according to claim 1, it is characterised in that to prepared The reappearance of sensor is tested, and fluorescence intensity fall less than 1%, think highly of by the sensing of preparation after continuous scanning 3000s Existing functional, stable performance；After being measured 90 days to the long-time stability of prepared sensor again, its electrochemistry hair Luminous intensity is reduced less than 10%, and the electrochemical luminescence sensor long-time stability of preparation are good.
CN201610489344.2A 2016-06-27 2016-06-27 A kind of preparation method of solid-state electrochemistry illumination sensor Active CN105911122B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610489344.2A CN105911122B (en) 2016-06-27 2016-06-27 A kind of preparation method of solid-state electrochemistry illumination sensor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610489344.2A CN105911122B (en) 2016-06-27 2016-06-27 A kind of preparation method of solid-state electrochemistry illumination sensor

Publications (2)

Publication Number Publication Date
CN105911122A CN105911122A (en) 2016-08-31
CN105911122B true CN105911122B (en) 2018-02-16

Family

ID=56758779

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610489344.2A Active CN105911122B (en) 2016-06-27 2016-06-27 A kind of preparation method of solid-state electrochemistry illumination sensor

Country Status (1)

Country Link
CN (1) CN105911122B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108918483B (en) * 2018-05-08 2020-10-30 青岛大学 Method for preparing molecular imprinting sensor by photocatalytic RAFT polymerization and application thereof
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
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
CN114994132B (en) * 2022-08-01 2022-11-01 成都工业学院 Method for testing regulation and control of Rh-N4-graphene hydrogen evolution performance by stress

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102530932A (en) * 2011-12-21 2012-07-04 青岛大学 Green and environmentally-friendly preparation method of graphene with low defect and large size
CN102585425A (en) * 2011-12-21 2012-07-18 青岛大学 Preparation method of temperature-sensitive controllable graphene-polymer composite material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102530932A (en) * 2011-12-21 2012-07-04 青岛大学 Green and environmentally-friendly preparation method of graphene with low defect and large size
CN102585425A (en) * 2011-12-21 2012-07-18 青岛大学 Preparation method of temperature-sensitive controllable graphene-polymer composite material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Graphene/tri-block copolymer composites prepared via RAFT polymerizations for dual controlled drug delivery via pH stimulation and biodegradation;Zhongqian Song等;《European Polymer Journal》;20150217;第69卷;第559–572页 *
RAFT活性聚合法制备聚苯乙烯;刘长玲等;《广州化工》;20151130;第43卷(第22期);第92-94页 *

Also Published As

Publication number Publication date
CN105911122A (en) 2016-08-31

Similar Documents

Publication Publication Date Title
CN105911122B (en) A kind of preparation method of solid-state electrochemistry illumination sensor
Ji et al. Physical removal of anions from aqueous media by means of a macrocycle-containing polymeric network
CN104772088B (en) A kind of preparation method of the tiny balloon polymer of covalent organic framework without template
Zhang et al. A molecularly imprinted polymer based on functionalized multiwalled carbon nanotubes for the electrochemical detection of parathion-methyl
Wang et al. Transport behaviors of anionic azo dyes at interface between surfactant-modified flax shives and aqueous solution: Synchrotron infrared and adsorption studies
CN107970788B (en) Preparation method of selective recognition and separation enoxacin molecular imprinting composite membrane material
CN105153420B (en) A kind of water-soluble porphyrin based polyalcohol of detectable heavy metal ion
CN104028007A (en) Imidazole ionic liquid capillary monolithic column, and making method and application thereof
CN107442152B (en) The preparation of the porous carbon microsphere of Fe/Co-NPS codope and its application in terms of organic pollutant removal
CN103406109A (en) Controllable and universal directional surface printing method and application of molecular printing polymer obtained via same
CN101264881B (en) Cyclodextrin-carbon nano tube derivatives and preparation method thereof
CN105566400B (en) Heterogeneous cobalt metal-organic framework and preparation and the application in field of waste water treatment
CN103272626A (en) Composite catalyst taking pulverized fuel ash floating beads as matrix supported heteropoly acid, and preparation method and application of composite catalyst
Fan et al. Preparation of a novel mixed non-covalent and semi-covalent molecularly imprinted membrane with hierarchical pores for separation of genistein in Radix Puerariae Lobatae
CN109776764A (en) A kind of super organic cross-linked polymeric object material, preparation method and application
CN108970584A (en) A kind of preparation method for the covalent organic nano piece of cation removing radioactivity anionic pollutant
CN105115947B (en) A kind of graphene quantum dot sensor and its application in terms of trinitrophenol is detected
CN107837796B (en) Bonded chromatographic column stationary phase
Yang et al. β-cyclodextrin grafted on lignin as inverse phase transfer catalyst for the oxidation of benzyl alcohol in H2O
CN105218765A (en) A kind of Preparation method and use of photoresponse intelligence trace mesoporous material
Lu et al. An active two-dimensional covalent organic framework for persulfate-assisted high efficiency photocatalytic degradation of rhodamine B
Cai et al. A graphene oxide-molybdenum disulfide composite used as stationary phase for determination of sulfonamides in open-tubular capillary electrochromatography
CN101612555A (en) A kind of stirring rod for whole molecularly imprinted polymer and preparation method thereof
Zhang et al. Preparation, application and development of poly (ionic liquid) microspheres
Yuan et al. Preparation of poly (styrene‐co‐allyl sulfonic acid) as a novel catalyst for the alcoholysis of dioscin

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant