CN109535494A - A kind of composite material and its preparation and application for detecting organic pollutant rhodamine b - Google Patents
A kind of composite material and its preparation and application for detecting organic pollutant rhodamine b Download PDFInfo
- Publication number
- CN109535494A CN109535494A CN201811332242.5A CN201811332242A CN109535494A CN 109535494 A CN109535494 A CN 109535494A CN 201811332242 A CN201811332242 A CN 201811332242A CN 109535494 A CN109535494 A CN 109535494A
- Authority
- CN
- China
- Prior art keywords
- rhodamine
- ferrocene
- composite material
- preparation
- electrode
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The present invention provides a kind of for detecting the composite material of pollutant rhodamine b, it is that first graphite oxide is connected with ferrocene by π-π effect, it is chitosan loaded to be restored to after above graphene oxide-ferrocene, synthesize redox graphene-ferrocene-chitosan.Using the electrode of composite material modification as working electrode, it is molten to be placed in [Fe (CN) 6] 4-/3- containing rhodamine b, it is 50mV/s sweeping speed, scanning range -0.2V ~ 0.6V condition carries out differential pulse voltammetry volt-ampere and identified: rhodamine b is in 0.001 μM ~ 70 μM concentration ranges, the size of differential pulse voltammetry dissolution peak current is in a linear relationship with rhodamine b concentration, as the increase peak current of rhodamine b concentration reduces, linear equation is Δ I=(7.619 ± 0.585)+(0.539 ± 0.016)C RhB。
Description
Technical field
The present invention relates to a kind of redox graphene-ferrocene-Chitosan Composites with excellent electrical
Preparation method;The invention further relates to concrete application of the composite material in detection rhodamine b, belong to electrochemical sensing identification skill
Art field.
Background technique
Rhodamine B (RhB) is organic dyestuff important in industry, the colorant being widely used as in textile and food, with
And the fluorescent dye in biology and analytical chemistry.However, RhB is harmful to human and animal, and has reproduction and development toxicity,
Neurotoxicity and carcinogenicity.RhB also has a negative impact to ecological environment as the main component of dyeing waste water.Nowadays, Luo Dan
Bright B is forbidden being used as edible pigment by Chinese food Drug Administration.Therefore, a kind of simple, quick and spirit is researched and developed
Quick detection method is particularly important.
Summary of the invention
The object of the present invention is to provide a kind of for detecting the preparation method of the composite material of pollutant rhodamine b.
It is used to detect the specific method in rhodamine b it is a further object of the present invention to provide above-mentioned composite material.
One, for detecting the preparation of the composite material of pollutant rhodamine b
(1) graphite oxide-ferrocene preparation: graphite oxide ultrasonic disperse is formed in ethanol-water mixed solvent uniformly outstanding
Supernatant liquid;The ethanol solution of ferrocene is added to suspension, is vigorously stirred 2 ~ 3h, stands 30 ~ 40min, separation, washing removes second
Alcohol, it is dry to get graphite oxide-ferrocene composite material.
In the ethanol-water mixed solvent, the volume ratio of second alcohol and water is 1:1 ~ 2:1;The matter of graphite oxide and ferrocene
Amount is than being 4:1 ~ 4:2.
(2) redox graphene-ferrocene-Chitosan Composites preparation: graphite oxide-ferrocene is dissolved in
In ionized water, it is ultrasonically treated 3 ~ 5h;Chitosan is dissolved in acetic acid, is then added in graphite oxide-solution of ferrocene, 60 ~ 70
2 ~ 3h is reacted at DEG C, and after sodium hydrate regulator solution pH to 10 ~ 12,2 ~ 3h is reacted at 85 ~ 100 DEG C;It crosses after the reaction was completed
Filter, dry, obtaining black solid is redox graphene-ferrocene-chitosan, is labeled as RGO-Fc-CS.
The mass ratio of redox graphene-ferrocene and chitosan is 1:1 ~ 1:2.
In step (1) (2), the drying is dry 8 ~ 10h in freeze drying box.
Two, redox graphene-ferrocene-Chitosan Composites structure
Fig. 1 is redox graphene prepared by the present invention-ferrocene-Chitosan Composites scanning electron microscope (SEM) photograph.It can from Fig. 1
To find out, redox graphene-ferrocene-chitosan has three-dimensional structure, and has more pore structure, pattern rule
Whole, even pore distribution has good dispersibility.This hole be conducive to the transmission of electronics so that composite material electric conductivity
Can have greatly improved.
In redox graphene-ferrocene-Chitosan Composites, graphite oxide acts on phase by π-π with ferrocene
Even, chitosan loaded to be restored to after above graphene oxide-ferrocene, synthesize redox graphene-ferrocene-shell
Glycan, composite material had not only remained the satisfactory electrical conductivity of redox graphene and ferrocene, but also had chitosan for Luo Dan
The sensitive detection property of bright b.
Three, composite material detection machine pollutant rhodamine b
1, ultraviolet detection rhodamine b
The rhodamine b for taking 50mM pure, which is attached in cuvette, carries out ultraviolet test, and reduction-oxidation graphite then is being added toward rhodamine b
The molar ratio of alkene-ferrocene-Chitosan Composites solution, composite material and rhodamine b are 1:0.2 ~ 1:5, in ultraviolet light
Under the conditions of, variation of the observation composite material in the absorbance of 555nm.
It can be seen that it is decline compared with pure rhodamine b that absorbance after composite material is added into rhodamine b solution
, this is because the effect of hydrogen bond has occurred between composite material and rhodamine b so that the decline of absorbance, this also into
One step shows composite material and is acted in rhodamine b so as to effectively detect rhodamine b.Fig. 2,3 are oxygen reduction
Graphite alkene-ferrocene-Chitosan Composites identify ultraviolet curve and linear relationship to rhodamine b.In composite material and sieve
The concentration molar ratio of red bright b is the ultraviolet absorptivity of composite material and the concentration of rhodamine b in the concentration range of 1:0.5 ~ 1:5
It is 1:1 in concentration molar ratio is that absorbance change value is maximum now as the changing value that concentration rises absorbance becomes larger, detection effect
Most preferably, then as the rising absorbance change value of concentration molar ratio reduces, detection effect weakens.
2, Differential Pulse Voltammetry detects rhodamine b
The building of the electrode RGO-Fc-CS/GCE of composite material modification: the composite material RGO-Fc-CS of above-mentioned preparation is dispersed in
In 95% ethyl alcohol of mass percent, 60 ~ 70min of ultrasound obtains equal phase dispersant liquid;Then equal phase dispersant liquid drop is coated in cleaned
The bare glassy carbon electrode surface of processing places the solvent evaporating completely for making electrode surface at room temperature, obtains composite material modification
Electrode RGO-Fc-CS/GCE, i.e. working electrode.
Rhodamine b is detected by electrochemical workstation: using the above-mentioned modified electrode RGO-Fc-CS/GCE for preparing as work
Electrode is placed in the [Fe (CN) containing rhodamine b6]4-/3-In solution (KCl comprising 0.1M), it is 50mV/s sweeping speed, scans model
- 0.2V ~ 0.6V condition progress differential pulse voltammetry volt-ampere is enclosed to be identified.Rhodamine b can be deposited under -0.6V ~ 0.2V voltage
To working electrode surface, prevent redox reaction is smoothly carried out from crossing;And then, working electrode is applied from negative to positive
Reverse potential carry out differential pulse voltammetry process in leaching, on differential pulse voltammetry figure it is seen that point and narrow dissolution peak;And foundation
The size of peak current is dissolved out to detect rhodamine b.
Fig. 4,5 are modified electrode RGO-Fc-CS/GCE for the rhodamine b differential pulse voltammetry volt-ampere curve detected and linear pass
System.From Fig. 4,5 as can be seen that as the result is shown as the concentration of composite material increases, peak point current is smaller, this illustrates sieve of absorption
Red bright b is more.For rhodamine b in 0.001 μM ~ 70 μM concentration ranges, differential pulse voltammetry dissolves out the size and rhodamine b of peak current
Concentration it is in a linear relationship, with rhodamine b concentration increase peak current reduce, linear equation be Δ I=(7.619 ± 0.585)
+(0.539±0.016)C RhB 。
Detailed description of the invention
Fig. 1 is redox graphene-ferrocene-Chitosan Composites scanning electron microscope (SEM) photograph.
Fig. 2 is that redox graphene-ferrocene-Chitosan Composites detect ultraviolet curve to rhodamine b
Fig. 3 is that redox graphene-ferrocene-Chitosan Composites are linear under the conditions of ultraviolet to rhodamine b detection
Relationship.
Fig. 4 is the differential pulse voltammetry volt-ampere curve that modified electrode RGO-Fc-CS/GCE detects rhodamine b.
Fig. 5 is that modified electrode RGO-Fc-CS/GCE detects the linear pass under differential pulse voltammetry volt-ampere curve for rhodamine b
System.
Specific embodiment
Below by specific example to redox graphene-ferrocene-Chitosan Composites preparation of the present invention and
The method etc. of detection rhodamine b is described further.
1, redox graphene-ferrocene-Chitosan Composites preparation
(1) preparation of graphite oxide: the process of first step pre-oxidation: under magnetic stirring by 1.25gK2S2O8And 1.25gP2O5
It is added at one time the dense H of 12.5mL2SO4In, 1g graphite powder is then added, mixed solution will be changed and be heated to 80 DEG C, stirred in magnetic force
It mixes down and is heated to reflux 5h, after cooling, the dilution of 200mL water, the neutrality being then filtered, washed, in 60 DEG C of vacuum are added into solution
Under the conditions of it is dry.The further oxidation process of second step: the graphite oxide of above-mentioned drying is weighed 1g, is scattered under condition of ice bath
In the nitration mixture (volume ratio of the concentrated sulfuric acid and phosphoric acid is 3:1) of the 120mL concentrated sulfuric acid and phosphoric acid, temperature is kept to be 0 ~ 5 DEG C and constantly stir
Lower addition 9g potassium permanganate is mixed, temperature is then risen into 50 DEG C of stirring 12h.System temperature is cooled to room temperature, is separately added into
The hydrogen peroxide of 200mL ice water 5mL30%, and be stirred continuously, the HCl of 5mL5% is added, is finally washed, filters, is dried to obtain
Graphite oxide.
(2) 100mg graphite oxide graphite oxide-ferrocene preparation: is dispersed in 30mL EtOH-DI water mixed liquor
In (ethyl alcohol and deionized water volume ratio 1:1), ultrasonic treatment form uniform suspension;10mL bis- is rapidly joined to suspension
Luxuriant iron ethanol solution (5mgmL-1) and be vigorously stirred 2 ~ 3h, stand 30 ~ 40min;Filtering, washing remove ethyl alcohol, are freeze-dried,
Obtain 120mg graphite oxide-ferrocene.
(3) redox graphene-ferrocene-chitosan preparation: 20mg graphite oxide-ferrocene is taken, 40mL is dissolved in
In deionized water, it is ultrasonically treated 3 ~ 4 hours;20mg chitosan is dissolved in 25mL acetic acid solution (0.1mol/L), is then added
It is reacted 2 ~ 3 hours into graphite oxide-solution of ferrocene, and at 60 ~ 70 DEG C;PH value of solution is adjusted using sodium hydroxide (1mol/L)
To 10 ~ 12(, the purpose is to reduce graphite oxides), 90 ~ 100 DEG C are then heated to, is then reacted again in oil bath 2 ~ 3 hours.Reaction
After the completion, it filters, freeze-drying obtains black solid redox graphene-ferrocene-chitosan (RGO-Fc-CS).
2, Electrochemical Detection rhodamine b
The preparation of modified electrode (RGO-Fc-CS/GCE): the above-mentioned 5mgRGO-Fc-CS being prepared is dispersed in 5mL ethyl alcohol
(95%) in, 60 ~ 70min of ultrasound obtains equal phase dispersant liquid.Then, take the 3 direct drop coatings of this dispersion liquid of μ L straight with microsyringe
The bare glassy carbon electrode surface that diameter is 3mm is (bare glassy carbon electrode before being modified, respectively with 0.3 μm and 0.05 μm on chamois leather
Al2O3Powder is polished to mirror surface, after washing surface dirt, is transferred in ultrasonic water bath successively with dehydrated alcohol, nitric acid (1:1, V/
V) and ultrapure water continuously washs 2min), keep the solvent of electrode surface complete finally, modified electrode to be placed to 5 ~ 8min at room temperature
Evaporation obtains the electrode RGO-Fc-CS/GCE of composite material modification, i.e. working electrode.
Rhodamine b is detected by electrochemistry station:
(1) preparation of sample solution: the concentration for preparing sample solution rhodamine b is 50 μM/L, and compound concentration is 10 ~ 350 μM/L
RGO-Fc-CS;
(2) Electrochemical Detection: modified electrode RGO-Fc-CS/GCE is placed in the [Fe containing 50 μM/L rhodamine b as working electrode
(CN)6]4-/3-Solution (KCl comprising 0.1M) is 50mV/s sweeping speed, and scanning range -0.2V ~ 0.6V condition carries out showing difference
Pulse Voltammetry is identified.The results show that the dissolution peak current of differential pulse voltammetry voltammogram is 34 μ A, dissolved out further according to differential pulse voltammetry
The size of peak current with RGO-Fc-CS concentration increase peak current reduce, linear equation be Δ I=(7.619 ± 0.585)+
(0.539±0.016)C RhB, the rhodamine b concentration for calculating detection is 49.34 μM/L and theoretical value differs very little, this explanation
Composite material RGO-Fc-CS has extraordinary detection to rhodamine b.
Claims (6)
1. the preparation method for the composite material for detecting pollutant rhodamine b, comprising the following steps:
(1) graphite oxide-ferrocene preparation: graphite oxide ultrasonic disperse is formed in ethanol-water mixed solvent uniformly outstanding
Supernatant liquid;The ethanol solution of ferrocene is added to suspension, is vigorously stirred 2 ~ 3h, stands 30 ~ 40min, separation, washing removes second
Alcohol, it is dry to get graphite oxide-ferrocene composite material;
(2) graphite oxide-ferrocene redox graphene-ferrocene-Chitosan Composites preparation: is dissolved in deionization
In water, it is ultrasonically treated 3 ~ 5h;Chitosan is dissolved in acetic acid, is then added in graphite oxide-solution of ferrocene, at 60 ~ 70 DEG C
2 ~ 3h is reacted, after sodium hydrate regulator solution pH to 10 ~ 12,2 ~ 3h is reacted at 85 ~ 100 DEG C;It filters, does after the reaction was completed
Dry, obtaining black solid is redox graphene-ferrocene-chitosan, is labeled as RGO-Fc-CS.
2. as described in claim 1 for detecting the preparation method of the composite material of pollutant rhodamine b, it is characterised in that: step
Suddenly in the ethanol-water mixed solvent of (1), the volume ratio of second alcohol and water is 1:1 ~ 2:1.
3. as described in claim 1 for detecting the preparation method of the composite material of pollutant rhodamine b, it is characterised in that: step
Suddenly in (1), the mass ratio of graphite oxide and ferrocene is 4:1 ~ 4:2.
4. as described in claim 1 for detecting the preparation method of the composite material of pollutant rhodamine b, it is characterised in that: step
Suddenly in (2), the mass ratio of redox graphene-ferrocene and chitosan is 1:1 ~ 1:2.
5. as described in claim 1 for detecting the preparation method of the composite material of pollutant rhodamine b, it is characterised in that: step
Suddenly in (1) (2), the drying is dry 8 ~ 10h in freeze drying box.
6. the composite material of method preparation as described in claim 1 is for detecting pollutant rhodamine b, comprising:
(1) building of modified electrode: redox graphene-ferrocene-Chitosan Composites RGO-Fc-CS is dispersed in
In 95% ethyl alcohol, 60 ~ 70min of ultrasound obtains equal phase dispersant liquid;This equal phase dispersant liquid drop is coated in the naked glass carbon of cleaned processing again
Electrode surface places the electrode for modifying the solvent evaporating completely of electrode surface to get composite material at room temperature;
(2) it Electrochemical Detection rhodamine b: using the electrode of composite material modification as working electrode, is carried out by electrochemical workstation
Detection: the electrode that above-mentioned composite material is modified is placed in [the Fe (CN) containing rhodamine b as working electrode6]4-/3-Solution
In, it is 50mV/s sweeping speed, scanning range -0.2V ~ 0.6V condition carries out differential pulse voltammetry volt-ampere and identified: rhodamine b exists
In 0.001 μM ~ 70 μM concentration ranges, differential pulse voltammetry dissolves out the in a linear relationship of size and the rhodamine b concentration of peak current, with
Rhodamine b concentration increase peak current reduce, linear equation are as follows:
ΔI=(7.619±0.585)+(0.539±0.016)C RhB。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811332242.5A CN109535494B (en) | 2018-11-09 | 2018-11-09 | Composite material for detecting organic pollutant rhodamine b and preparation and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811332242.5A CN109535494B (en) | 2018-11-09 | 2018-11-09 | Composite material for detecting organic pollutant rhodamine b and preparation and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109535494A true CN109535494A (en) | 2019-03-29 |
CN109535494B CN109535494B (en) | 2021-03-30 |
Family
ID=65846608
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811332242.5A Expired - Fee Related CN109535494B (en) | 2018-11-09 | 2018-11-09 | Composite material for detecting organic pollutant rhodamine b and preparation and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109535494B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103063728A (en) * | 2012-12-30 | 2013-04-24 | 南京师范大学 | Electrochemical method for simultaneous determination of tetrachlorocatechol and tetrachlorohydroquinone based on graphene/chitosan-modified electrode |
CN108726515A (en) * | 2018-05-31 | 2018-11-02 | 西北师范大学 | Preparation method with three-dimensional structure redox graphene-ferrocene composite material |
CN109369974A (en) * | 2018-11-08 | 2019-02-22 | 西北师范大学 | A kind of redox graphene-ferrocene-Chitosan Composites preparation method |
-
2018
- 2018-11-09 CN CN201811332242.5A patent/CN109535494B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103063728A (en) * | 2012-12-30 | 2013-04-24 | 南京师范大学 | Electrochemical method for simultaneous determination of tetrachlorocatechol and tetrachlorohydroquinone based on graphene/chitosan-modified electrode |
CN108726515A (en) * | 2018-05-31 | 2018-11-02 | 西北师范大学 | Preparation method with three-dimensional structure redox graphene-ferrocene composite material |
CN109369974A (en) * | 2018-11-08 | 2019-02-22 | 西北师范大学 | A kind of redox graphene-ferrocene-Chitosan Composites preparation method |
Non-Patent Citations (3)
Title |
---|
王欢等: "电化学法研究罗丹明B与壳聚糖的相互作用", 《分析试验室》 * |
谢冬香等: "壳聚糖-多壁碳纳米管/二茂铁修饰玻碳电极的电催化研究", 《功能材料》 * |
黄静: "基于石墨烯构建的葡萄糖生物传感器及其应用研究", 《中国优秀硕士学位论文全文数据库 信息科技辑》 * |
Also Published As
Publication number | Publication date |
---|---|
CN109535494B (en) | 2021-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Pang et al. | Synthesis and factor affecting on the conductivity of polypyrrole: a short review | |
Chen et al. | Highly stable nickel hexacyanoferrate nanotubes for electrically switched ion exchange | |
Gao et al. | Superhydrophobic “wash free” 3D nanoneedle array for rapid, recyclable and sensitive SERS sensing in real environment | |
CN1323199C (en) | Preparation method of conductive polymer polyanilinc nano fiber | |
CN103983681B (en) | A kind of for electrochemical sensor detecting heavy metal and its preparation method and application | |
CN107235486B (en) | The preparation method of water-soluble graphene | |
Kastner et al. | Redox-active organic–inorganic hybrid polyoxometalate micelles | |
CN108726515A (en) | Preparation method with three-dimensional structure redox graphene-ferrocene composite material | |
JP2011505441A (en) | Production and use of novel polyaniline for water treatment | |
CN105752975B (en) | The method that electron beam irradiation prepares fluorescence graphene quantum dot | |
WO2023142668A1 (en) | Method for preparing nitrogen-doped carbon dot-reduced graphene oxide composite material and use thereof | |
CN104399415B (en) | A kind of preparation method of core-shell type graphene oxide/silver composite material | |
CN109916973A (en) | A kind of Graphite alkene-MOFs composite material, its preparation and application | |
CN109781826A (en) | A kind of preparation and application of rGO-PTCA-CS composite material | |
CN108318554A (en) | A kind of Electrochemical Detection graphene printing paper electrode and preparation method thereof | |
Li et al. | Selective detection of fenaminosulf via a molecularly imprinted fluorescence switch and silver nano-film amplification | |
CN109369974A (en) | A kind of redox graphene-ferrocene-Chitosan Composites preparation method | |
Harshavardhan et al. | Synthesis of Tin oxide nanoparticles using Nelumbo nucifera leaves extract for electrochemical sensing of dopamine | |
CN107653458A (en) | A kind of high-ratio surface phosphorus modifies Co3O4The preparation method of compound | |
CN109535494A (en) | A kind of composite material and its preparation and application for detecting organic pollutant rhodamine b | |
Wei et al. | An ultrasensitive ponceau 4R detection sensor based on molecularly imprinted electrode using pod-like cerium molybdate and multi-walled carbon nanotubes hybrids | |
CN109836577A (en) | A kind of preparation and application of redox graphene-poly-dopamine-lysine composite material | |
CN111334085B (en) | Graphene modification method of phthalocyanine blue pigment | |
Lv et al. | A post-oxidation strategy for the synthesis of graphene/carbon nanotube-supported polyaniline nanocomposites as advanced supercapacitor electrodes | |
CN100480298C (en) | Chemical-oxidation direct preparing method for polyamino anthaquinone nano particles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210330 Termination date: 20211109 |