CN108107091B - A kind of preparation method and application of chirality MOF membrane material - Google Patents
A kind of preparation method and application of chirality MOF membrane material Download PDFInfo
- Publication number
- CN108107091B CN108107091B CN201711472654.4A CN201711472654A CN108107091B CN 108107091 B CN108107091 B CN 108107091B CN 201711472654 A CN201711472654 A CN 201711472654A CN 108107091 B CN108107091 B CN 108107091B
- Authority
- CN
- China
- Prior art keywords
- mof
- preparation
- chiral
- chirality
- membrane material
- 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.)
- Expired - Fee Related
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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method and application of chirality MOF membrane material, more particularly to a kind of preparation method and application of foam copper loaded chiral Metal-organic frame MOF crystal composite material, belong to the technical fields such as nano material, metal organic complex nano material and analytical chemistry.It has main steps that L-Aspartic acid is blended with the blended liquid of water with the aqueous solution of potassium peroxydisulfate, heating and refluxing to dissolve, continuously add the foam copper of ethyl alcohol and activation, and it is heated to reflux 6h, foam copper loaded chiral Metal-organic frame MOF crystal composite material, i.e. chirality MOF membrane material is made.Chirality MOF membrane material sensor is constructed using the composite material, for the detection of L-Histidine Enantiomeric excess, preparation method is simple, easy to operate, and chiral detection effect is significant.
Description
Technical field
The present invention relates to a kind of preparation method and application of chirality MOF membrane material, and in particular to foam copper loaded chiral gold
The preparation method and application for belonging to organic framework MOF crystal composite material, belong to nano material, metal organic complex nanometer material
The technical fields such as material and analytical chemistry.
Background technique
The property that compound molecule and its mirror image can not overlap completely is known as chirality, chirality be nature essential attribute it
One.Chiral metal organic framework materials (MOFs) are by chiral organic bridge ligand and metal ion or metal cluster by from group
Periodically ordered porous crystalline material made of dress.Chiral MOFs is as a kind of new function material, because it is with high ratio table
The features such as area, topological structure abundant, the pore structure of rule and modifiable channel surfaces, makes it in chiral catalysis, passes
Many fields such as sense technology have broad application prospects.
In recent years, many researchers are based on metal ion and chiral organic ligand has synthesized some chirality MOFs crystal materials
Material, but usually structure is complicated for chiral organic ligand used, and the rare report of the technological development for being used for chiral electrochemical recognition
Road.
Summary of the invention
Technical assignment of the invention first is that in order to make up for the deficiencies of the prior art, a kind of foam copper loaded chiral gold is provided
Belong to the preparation method of organic framework MOF crystal composite material, this method is raw materials used at low cost, and preparation process is simple, reaction
Low energy consumption, has prospects for commercial application.
The two of technical assignment of the invention are to provide the foam copper loaded chiral Metal-organic frame MOF crystal composite wood
Composite material is used for the content of efficient detection D-His and L-Histidine enantiomer by the purposes of material, the detecting instrument at
This is low, analysis efficiency is high, easy to operate, and operating technology requires low.
Technical scheme is as follows:
1. a kind of preparation method of chirality MOF membrane material, steps are as follows:
The L-Aspartic acid of 0.090-0.110g is blended with 3-3.5 mL water, obtained L-Aspartic acid is blended with water
Liquid；0.14-0.16 g potassium peroxydisulfate is dissolved in 3-3.5 mL water, the aqueous solution of potassium peroxydisulfate is made；
After L-Aspartic acid is blended with the aqueous solution of the blended liquid of water and potassium peroxydisulfate, after heating and refluxing to dissolve, it is added
The foam copper of 3-4 mL ethyl alcohol and activation continues to be heated to reflux 6h, after foam carbon/carbon-copper composite material is taken out, uses water and ethyl alcohol respectively
Wash 3 times, dry, obtained foam copper loaded chiral Metal-organic frame MOF crystal composite material, i.e. chirality MOF membrane material.
The foam copper loaded chiral Metal-organic frame MOF crystal composite material, the chemical formula of MOF are [Cu (L-
Asp)] n, an asymmetric structural unit are by a Cu2+, a L-Aspartic acid bear sub- L-Asp2-Composition；It is described
L-Asp2-Structural formula is as follows:
The MOF crystal is nano-sheet crystals.
The foam copper of the activation is that the foam copper of the cm of 0.5cm × 0.5 is immersed in 9.5-10.5 mL, mass fraction
2 dryings are washed with ethyl alcohol and are made with distilled water flushing 3 times for 10min in 9% dilute hydrochloric acid, then ultrasound 5-10min.
2. chiral MOF membrane material the answering as electrochemical sensing detection enantiomer of preparation method preparation as described above
With steps are as follows:
(1) electrochemistry chiral sensor is prepared
Chiral MOF membrane material prepared by claim 1 is reference electrode, platinum as working electrode, saturated calomel electrode
Silk electrode is to be connected on electrochemical workstation to electrode, has been made based on chirality MOF membrane material electrochemistry chiral sensor；
(2) D-His and L-Histidine enantiomer are detected
Using pH 7.0,0.1 mol L-1PBS buffer solution, prepare the D-His of serial various concentration respectively
With L-Histidine standard solution, distinguished using electrochemistry chiral sensor made from step (1) using differential pulse voltammetry
The D-His of various concentration and the current value of L-Histidine standard solution are measured, is drawn based on chirality MOF thin-film material electrification
Learn the D-His and L-Histidine enantiomer working curve of chiral sensor；D-His or L-Histidine sample are dissolved in pH
7.0、 0.1 mol• L-1PBS buffer solution in, using differential pulse voltammetry, measure its current value, it is bent based on work
Line obtains the content of D-His and L-Histidine enantiomer in sample.
Chirality MOF membrane material electrochemistry chiral sensor is to the detection range of D-His and L-Histidine solution
0.1-1.0×10-10g/mL。
The beneficial technical effect of the present invention is as follows:
(1) preparation method of foam copper loaded chiral Metal-organic frame MOF crystal composite material of the present invention, foam copper
It is not only substrate, due to joined potassium peroxydisulfate in reaction system, potassium peroxydisulfate and foam copper occur redox reaction, become
Slow release Cu2 +Cu on ion source, aspartic acid anion and foam copper2 +Complexation reaction generates foam copper load chemistry
Formula is the MOF crystal composite material of [Cu (L-Asp)] n, and this method synthesis process is simple；In addition the L-Aspartic acid used is matched
Body is inexpensive；So that the preparation method is easy to industrialize.
(2) chirality MOF membrane material, i.e. foam copper loaded chiral Metal-organic frame MOF crystal composite material, directly
As working electrode for chiral detection L-Histidine enantiomer, avoids and MOF crystal is supported on glass-carbon electrode with binder
Caused secondary operation bring defect；The synergistic effect of foam copper electronic conductor and chirality MOF, so that being based on the composite material
The chiral sensor of preparation successfully detects the content of L-Histidine chiral enantiomer, and has quick response, detection range
Width, high sensitivity, it is easy to operate, time saving the features such as.
Specific embodiment
The present invention will be further described below with reference to examples, but protection scope of the present invention is not only limited to implement
Example, professionals in the field change to made by technical solution of the present invention, are within the scope of protection of the invention interior.
A kind of preparation method of the chirality MOF membrane material of embodiment 1.
The L-Aspartic acid of 0.090 g is blended with 3 mL water, the blended liquid of L-Aspartic acid and water is made；By 0.14
G potassium peroxydisulfate is dissolved in 3 mL water, and the aqueous solution of potassium peroxydisulfate is made；By the blended liquid and potassium peroxydisulfate of L-Aspartic acid and water
After aqueous solution is blended, after heating and refluxing to dissolve, the foam copper of 3 mL ethyl alcohol and activation is added, continues to be heated to reflux 6h, by foam
After carbon/carbon-copper composite material takes out, respectively with water and ethanol washing 3 times, dry, foam copper loaded chiral Metal-organic frame is made
MOF crystal composite material, i.e. chirality MOF membrane material.
The MOF crystal is nano-sheet crystals；
The foam copper of the activation is that the foam copper of the cm of 0.5cm × 0.5 is immersed in 9.5 mL, mass fraction 9%
Dilute hydrochloric acid in 10min, then ultrasound 5min washed 2 dryings with distilled water flushing 3 times with ethyl alcohol and be made.
A kind of preparation method of the chirality MOF membrane material of embodiment 2.
The L-Aspartic acid of 0.110g is blended with 3.5 mL water, the blended liquid of L-Aspartic acid and water is made；It will
0.16 g potassium peroxydisulfate is dissolved in 3.5 mL water, and the aqueous solution of potassium peroxydisulfate is made；
After L-Aspartic acid is blended with the aqueous solution of the blended liquid of water and potassium peroxydisulfate, after heating and refluxing to dissolve, it is added 4
The foam copper of mL ethyl alcohol and activation continues to be heated to reflux 6h, after foam carbon/carbon-copper composite material is taken out, uses water and ethanol washing respectively
3 times, dry, obtained foam copper loaded chiral Metal-organic frame MOF crystal composite material, i.e. chirality MOF membrane material.
The MOF crystal is nano-sheet crystals.
The foam copper of the activation is by the foam copper of the cm of 0.5cm × 0.5, is immersed in 10.5 mL, mass fraction is
10min in 9% dilute hydrochloric acid, then ultrasound 10min are washed 2 dryings with ethyl alcohol and are made with distilled water flushing 3 times.
A kind of preparation method of the chirality MOF membrane material of embodiment 3.
The L-Aspartic acid of 0.100g is blended with 3.2 mL water, the blended liquid of L-Aspartic acid and water is made；It will
0.15 g potassium peroxydisulfate is dissolved in 3.3 mL water, and the aqueous solution of potassium peroxydisulfate is made；By the blended liquid and mistake of L-Aspartic acid and water
After the aqueous solution of potassium sulfate is blended, after heating and refluxing to dissolve, the foam copper of 3.5 mL ethyl alcohol and activation is added, continues to be heated to reflux
6h, after foam carbon/carbon-copper composite material is taken out, respectively with water and ethanol washing 3 times, dry, foam copper loaded chiral metal, which is made, to be had
Machine frame object MOF crystal composite material, i.e. chirality MOF membrane material.
The MOF crystal is nano-sheet crystals.
The foam copper of the activation is that the foam copper of the cm of 0.5cm × 0.5 is immersed in 10 mL, mass fraction 9%
Dilute hydrochloric acid in 10min, then ultrasound 7min washed 2 dryings with distilled water flushing 3 times with ethyl alcohol and be made.
Embodiment 4
Foam copper loaded chiral Metal-organic frame MOF crystal composite material, the chemical formula of MOF described in embodiment 1-3
For [Cu (L-Asp)] n, an asymmetric structural unit is by a Cu2+, a L-Aspartic acid bear sub- L-Asp2-Group
At；The L-Asp2-Structural formula is as follows:
Embodiment 5
The chiral MOF membrane material of the preparation of preparation method described in embodiment 1-4 is as electrochemical sensing detection enantiomer
Using steps are as follows:
(1) electrochemistry chiral sensor is prepared
Chiral MOF membrane material prepared by claim 1 is reference electrode, platinum as working electrode, saturated calomel electrode
Silk electrode is to be connected on electrochemical workstation to electrode, has been made based on chirality MOF membrane material electrochemistry chiral sensor；
(2) D-His and L-Histidine enantiomer are detected
Using pH 7.0,0.1 mol L-1PBS buffer solution, prepare the D-His of serial various concentration respectively
With L-Histidine standard solution, distinguished using electrochemistry chiral sensor made from step (1) using differential pulse voltammetry
The D-His of various concentration and the current value of L-Histidine standard solution are measured, is drawn based on chirality MOF thin-film material electrification
Learn the D-His and L-Histidine enantiomer working curve of chiral sensor；D-His or L-Histidine sample are dissolved in pH
7.0、 0.1 mol• L-1PBS buffer solution in, using differential pulse voltammetry, measure its current value, it is bent based on work
Line obtains the content of D-His and L-Histidine enantiomer in sample.
The chirality MOF membrane material electrochemistry chiral sensor, to the detection range of D-His and L-Histidine solution
For 0.1-1.0 × 10-10g/mL。
Claims (4)
1. a kind of preparation method of chirality MOF membrane material, which is characterized in that preparation step is as follows:
The L-Aspartic acid of 0.090-0.110g is blended with 3.0-3.5mL water, the blended liquid of L-Aspartic acid and water is made；It will
0.14-0.16g potassium peroxydisulfate is dissolved in 3-3.5mL water, and the aqueous solution of potassium peroxydisulfate is made；
After L-Aspartic acid is blended with the aqueous solution of the blended liquid of water and potassium peroxydisulfate, after heating and refluxing to dissolve, 3-4mL is added
The foam copper of ethyl alcohol and activation continues to be heated to reflux 6h, after foam carbon/carbon-copper composite material is taken out, uses water and ethanol washing 3 respectively
It is secondary, dry, foam copper loaded chiral Metal-organic frame MOF crystal composite material, i.e. chirality MOF membrane material is made；It is described
Foam copper loaded chiral Metal-organic frame MOF crystal composite material, the chemical formula of MOF is [Cu (L-Asp)] n, not right
The structural unit claimed, is by a Cu2+, a L-Aspartic acid bear sub- L-Asp2-Composition；The L-Asp2-Structural formula is such as
Under:
2. the preparation method of chirality MOF membrane material as described in claim 1, which is characterized in that the foam copper of the activation is
By the foam copper of 0.5cm × 0.5cm, it is immersed in 9.5-10.5mL, 10min in the dilute hydrochloric acid that mass fraction is 9%, then ultrasound 5-
10min is washed 2 dryings with ethyl alcohol and is made with distilled water flushing 3 times.
3. the chiral MOF membrane material of preparation method preparation as described in claim 1 is as electrochemical sensing detection enantiomer
Using.
4. the application of electrochemical sensing detection enantiomer as claimed in claim 3, which is characterized in that steps are as follows:
(1) electrochemistry chiral sensor is prepared
Chiral MOF membrane material prepared by claim 1 is reference electrode, platinum filament electricity as working electrode, saturated calomel electrode
Extremely electrode is connected on electrochemical workstation, has been made based on chirality MOF membrane material electrochemistry chiral sensor；
(2) D-His and L-Histidine enantiomer are detected
Using pH 7.0,0.1molL-1PBS buffer solution, prepare the D-His and L- group ammonia of serial various concentration respectively
Sour standard solution, using electrochemistry chiral sensor made from step (1), using differential pulse voltammetry, measurement is different respectively
The D-His of concentration and the current value of L-Histidine standard solution are drawn and are passed based on chirality MOF thin-film material electrochemistry chirality
The D-His and L-Histidine enantiomer working curve of sensor；By D-His or L-Histidine sample be dissolved in pH7.0,
0.1mol·L-1PBS buffer solution in, using differential pulse voltammetry, measure its current value, be based on working curve, obtain sample
The content of D-His and L-Histidine enantiomer in product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711472654.4A CN108107091B (en) | 2017-12-29 | 2017-12-29 | A kind of preparation method and application of chirality MOF membrane material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711472654.4A CN108107091B (en) | 2017-12-29 | 2017-12-29 | A kind of preparation method and application of chirality MOF membrane material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108107091A CN108107091A (en) | 2018-06-01 |
| CN108107091B true CN108107091B (en) | 2019-09-27 |
Family
ID=62214509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711472654.4A Expired - Fee Related CN108107091B (en) | 2017-12-29 | 2017-12-29 | A kind of preparation method and application of chirality MOF membrane material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108107091B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111408414A (en) * | 2020-03-12 | 2020-07-14 | 济南大学 | CuO/Ce2O3Preparation method and application of hybrid chiral Cu-MOF core-shell nanocomposite |
| CN111413380A (en) * | 2020-03-12 | 2020-07-14 | 济南大学 | Preparation method and application of HKUST-1-based chiral composite material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0474870A (en) * | 1990-07-13 | 1992-03-10 | Ebara Yuujiraito Kk | Electroless copper plating solution |
| CN105126642A (en) * | 2015-07-27 | 2015-12-09 | 北京工业大学 | Preparation of metal organic framework membrane and application in gas separation |
| CN105348198A (en) * | 2015-09-29 | 2016-02-24 | 中能科泰（北京）科技有限公司 | Metal organic framework film and preparation method therefor |
| CN106178982A (en) * | 2016-07-21 | 2016-12-07 | 北京工业大学 | A kind of preparation method of the metal organic framework film inverting based on subcarbonate |
| CN106229465A (en) * | 2016-08-18 | 2016-12-14 | 长安大学 | A kind of lithium ion battery negative based on 1,4 naphthalene diacid cobalts and preparation method thereof |
| CN106442686A (en) * | 2016-09-12 | 2017-02-22 | 济南大学 | Chiral metal organic framework polymer sensor as well as preparation and application thereof |
-
2017
- 2017-12-29 CN CN201711472654.4A patent/CN108107091B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0474870A (en) * | 1990-07-13 | 1992-03-10 | Ebara Yuujiraito Kk | Electroless copper plating solution |
| CN105126642A (en) * | 2015-07-27 | 2015-12-09 | 北京工业大学 | Preparation of metal organic framework membrane and application in gas separation |
| CN105348198A (en) * | 2015-09-29 | 2016-02-24 | 中能科泰（北京）科技有限公司 | Metal organic framework film and preparation method therefor |
| CN106178982A (en) * | 2016-07-21 | 2016-12-07 | 北京工业大学 | A kind of preparation method of the metal organic framework film inverting based on subcarbonate |
| CN106229465A (en) * | 2016-08-18 | 2016-12-14 | 长安大学 | A kind of lithium ion battery negative based on 1,4 naphthalene diacid cobalts and preparation method thereof |
| CN106442686A (en) * | 2016-09-12 | 2017-02-22 | 济南大学 | Chiral metal organic framework polymer sensor as well as preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 基于氨基酸的手性金属-有机框架材料的合成与性质研究;郑俊平;《中国优秀硕士学位论文全文数据库（工程科技I辑）》;20170615(第6期);第一章 * |
| 金属有机框架物制备及其油水分离性能的研究;王洒洒 等;《中国化学会第30届学术年会摘要集-第六分会：金属有机框架化学》;20160701;摘要 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108107091A (en) | 2018-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107589159B (en) | A kind of preparation method and application of chirality MOF nanofiber-graphene hybrid material | |
| US10871463B2 (en) | Preparation method based on simultaneous package of target substance and synthesis of MOFs with redox activity | |
| Gan et al. | One-step electrochemical approach for the preparation of graphene wrapped-phosphotungstic acid hybrid and its application for simultaneous determination of sunset yellow and tartrazine | |
| Setoudeh et al. | Zeolitic imidazolate frameworks and cobalt-tannic acid nanocomposite modified carbon paste electrode for simultaneous determination of dopamine, uric acid, acetaminophen and tryptophan: Investigation of kinetic parameters of surface electrode and its analytical performance | |
| CN106442686B (en) | A kind of chiral metal organic framework polymer sensor and its preparation method and application | |
| CN107490611B (en) | Polyaniline hybridized material of a kind of chirality MOF- and its preparation method and application | |
| CN107490610B (en) | A kind of chirality MOF- graphene hybrid material and its preparation method and application | |
| CN107442170B (en) | A kind of chirality MOF composite catalyst and its preparation method and application | |
| CN108144620A (en) | Foamed nickel supported composite Nano metal oxide electrode material preparation method | |
| CN103926294A (en) | Preparation and application of CS/IL-GR modified bovine serum albumin molecular imprinting electrode | |
| CN110483798B (en) | Preparation method and application of graphene oxide @ chiral Ni-MOF hybrid material | |
| CN108970642A (en) | A kind of carbon dots adulterate the preparation method and application of rich nitrogen MOF nano-chip arrays catalyst | |
| CN108107091B (en) | A kind of preparation method and application of chirality MOF membrane material | |
| Fu et al. | Electrochemiluminescence sensor for dopamine with a dual molecular recognition strategy based on graphite-like carbon nitride nanosheets/3, 4, 9, 10-perylenetetracarboxylic acid hybrids | |
| CN109265698A (en) | A kind of MOF/ carbon dots chiral hybrid material and its preparation method and application | |
| CN107238651B (en) | Preparation method of electrochemical sensor for detecting dopamine | |
| CN101793862B (en) | L-cysteine/chitosan-modified electrochemical sensor and use thereof | |
| CN103257176B (en) | Method for simultaneously detecting three isomers of benzenediol on basis of sensor of thionine functionalized carbon nanotube | |
| CN103487492A (en) | Electrochemical sensor for detecting trace amount of bisphenol A, manufacturing method thereof and application | |
| Wu et al. | Nanohybrid sensor for simple, cheap, and sensitive electrochemical recognition and detection of methylglyoxal as chemical markers | |
| Dong et al. | Flexible carbon fiber cloth supports decorated with cerium metal-organic frameworks and multi-walled carbon nanotubes for simultaneous on-site detection of Cd2+ and Pb2+ in food and water samples | |
| CN104792842A (en) | Preparation method and application of binuclear ruthenium complex film | |
| CN102520041B (en) | Method for preparing amino functional multiporous silica-based composite material for ion detection | |
| CN109752433A (en) | Nickel phosphate/Co-MOFs composite material and preparation method and application thereof | |
| CN108061751A (en) | A kind of method using molecular imprinting electrochemical detection Mancozeb |
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: 20190927 Termination date: 20211229 |