CN107677659A - Application of the dione pyrrolo-pyrrole dyestuff in the detection of trace bivalent cupric ion - Google Patents
Application of the dione pyrrolo-pyrrole dyestuff in the detection of trace bivalent cupric ion Download PDFInfo
- Publication number
- CN107677659A CN107677659A CN201710892485.3A CN201710892485A CN107677659A CN 107677659 A CN107677659 A CN 107677659A CN 201710892485 A CN201710892485 A CN 201710892485A CN 107677659 A CN107677659 A CN 107677659A
- Authority
- CN
- China
- Prior art keywords
- pyrrole
- detection
- dione
- pyrrolo
- dyestuff
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
-
- 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
Abstract
The invention discloses a kind of application of dione pyrrolo-pyrrole dyestuff in the detection of trace bivalent cupric ion.Dione pyrrolo-pyrrole dyestuff energy and Cu2+Radical cation is quickly generated, is changed so as to produce ultraviolet-visible absorption spectroscopy, so as to realize Cu2+Ultraviolet detection, have the response time fast, detection sensitivity is high, the characteristics of strong antijamming capability.The Cu of dione pyrrolo-pyrrole dyestuff structure2+Detection probe can be widely applied to the fields such as environmental project, biological detection.
Description
Technical field
The present invention relates to Cu2+Detection method, more particularly to a kind of special dione pyrrolo-pyrrole dyestuff, it can be with
Cu2+Generation specific reaction generates free radical molecule, and the ultraviolet-visible absorption spectroscopy of dione pyrrolo-pyrrole dyestuff occurs
Change, Cu is built by dione pyrrolo-pyrrole dyestuff2+Detection probe, realize trace Cu2+Detection, belong to sensing technology
Field.
Background technology
Adult needs to absorb a certain amount of copper (2mg/ days) daily, but newest research shows, long-term Excess free enthalpy copper
It may be made to accumulate in the brain, so as to damage brain blood barrier, it is senile dementia to trigger Alzheimer's disease
(Barnham,K.J.；Bush,A.I.Chemical Society Reviews 2014,43,6727-6749).Industrial quick hair
Exhibition exacerbates heavy metal environmental pollution, the food and water source of the mankind, or even air, all influenced to different extents.So copper
Ion monitoring work meaning is great, and chemical sensor can preferably meet monitoring needs and (Wu, X.M. in widespread attention；
Guo,Z.Q.；Wu,Y.Z.；Zhu,S.Q.；James,T.D.；Zhu,W.H.Acs Applied Materials&Interfaces
2013,5,12215-12220)。
Pyrrolo-pyrrole-dione (DPP) class dyestuff is a kind of development ripe commercial dyes earlier, and raw material is cheap and easy to get, right
Light, good thermal stability.Because pyrrolo-pyrrole-dione (DPP) class dyestuff has higher fluorescence quantum yield, larger rubs
Your extinction coefficient, there is good absorption in visible region, therefore, its had a wide range of applications in photoelectric functional material field (Li,
Y.N.；Sonar,P.；Murphy,L.；Hong,W.Energy&Environmental Science 2013,6,1684-
1710).But due to the water solubility of dione pyrrolo-pyrrole dyestuff extreme difference, its superior optics be can apply into ion chemistry and passed
Research very rare (Kaur, the M. of sense；Choi,D.H.Chemical Society Reviews 2015,44,58-77).In
State's patent (publication number CN 104818013B) discloses a kind of Diketopyrrolopyrrolederivative derivative in detection Hg2+In application, its
A kind of Diketopyrrolopyrrolederivative derivative is specifically disclosed to Hg2+Acted on selective complexation, and legibility is complexed, can conduct
Hg2+Identify that material is applied to prepare Hg in the detection aqueous solution2+Fluorescent optical sensor, obtained fluorescent optical sensor be used for detect Hg2+
With can visually identify, high sensitivity is reusable, and it has stronger Hg2+Selectivity, Ag+、Pb2+、Cu2+、Cr3+、Mn2 +、Fe3+、Co2+、Ni2+、Zn2+、Cd2+、Al3+Deng cation to Hg2+Detect noiseless, the fluorescent optical sensor can be widely applied to ring
The fields such as border engineering, biological detection.At present, and have not seen that dione pyrrolo-pyrrole dyestuff is used for selective enumeration method Cu2+Phase
Close report.
The content of the invention
For existing trace Cu2+The deficiencies of response time existing for detection technique is grown, and selectivity is not high, mesh of the invention
Be to be to provide a kind of dione pyrrolo-pyrrole dyestuff as Cu2+The application of detection probe, dione pyrrolo-pyrrole dye
Material can be to Cu2+Carry out quick, selectivity and sensitivity identification, it is possible to achieve Cu2+Ultraviolet detection, particularly suitable for detect it is molten
The Cu of trace in liquid system2+, it is with a wide range of applications.
In order to reach above-mentioned technical purpose, the invention provides a kind of dione pyrrolo-pyrrole dyestuff in trace Cu2+Inspection
Application in survey, using the dione pyrrolo-pyrrole dyestuff with the structure of formula 1 as Cu2+Detection probe application；
Wherein,
R1And R2Be independently selected from phenyl, phenyl derivatives (can be the phenyl containing electron donating group, such as alkyl substituted benzene
Base, alkoxy substituted phenyl etc.), thienyl, furyl or other conjugation groups；
R3And R4Being independently selected from H, alkyl, alkyloxy-ethers chain, (such as oligoethylene glycol, oxygen atomicity is no more than 10) or other soft
Property group.
Preferable scheme, R1And R2It is selected from thienyl or furyl；R3And R4It is selected from hydrogen or alkyl.
More preferably scheme, the alkyl are C1~C20Alkyl.
Further preferred scheme, the dione pyrrolo-pyrrole dyestuff have the structure of 2~formula of formula 4：
Preferable scheme, the dione pyrrolo-pyrrole dyestuff and Cu2+Generation specific chemical reaction generation pyrrolo-
Pyrroledione radical cation and Cu+。
More preferably scheme, the dione pyrrolo-pyrrole dyestuff by with Cu2+The front and rear ultravioletvisible absorption of reaction
Spectrum changes to realize Cu2+Identification.
In technical scheme, in acetonitrile solution, dione pyrrolo-pyrrole dyestuff energy and Cu2+Rapid reaction,
Pyrrolo-pyrrole-dione free radical molecule is generated, the change of ultraviolet-visible absorption spectroscopy is produced, reaches to Cu2+Quick identification mesh
's.
Preferable scheme, the dione pyrrolo-pyrrole dyestuff is in Ag+、Pb2+、Hg2+、Cr3+、Mn2+、Fe3+、Co2+、Ni2 +、Zn2+、Cd2+、Al3+、K+、Na+At least one of and Cu2+Selective recognition Cu in solution system coexists2+.Pyrrolopyrrole two
Ketone dyestuff and Cu2+Specific recognition capability is strong, is not disturbed by other metal ions, can identify micro- in hybrid metal ion
The Cu of amount2+。
More preferably scheme, the solution system include acetonitrile.
The dione pyrrolo-pyrrole dyestuff of the present invention is with the unmodified furyl of N atoms and thienyl pyrrolo- pyrrole
It is raw material (purchasing in Shanghai Aladdin biochemical technology limited company) to cough up dione molecule, passes through the step with halogenated compound
Substitution reaction is prepared.
Technical scheme chemical sensor rely primarily on the lactam structure of dione pyrrolo-pyrrole dyestuff with
Cu2+Ultraviolet-visible absorption spectroscopy change caused by specific chemical reaction comes to the Cu in system2+Detected.
Compared with the prior art, the advantageous effects that technical scheme is brought：
1st, dione pyrrolo-pyrrole dyestuff provided by the invention can be with Cu2+Fast reaction generates radical cation, band
Carry out the color change that naked eyes can be sentenced.
2nd, dione pyrrolo-pyrrole dyestuff provided by the invention is to Cu2+Identification there is high sensitivity, suitable for solution
Trace Cu in system2+Detection.
3rd, dione pyrrolo-pyrrole dyestuff provided by the invention is to Cu2+Response there is preferable selectivity, in Ag+、
Pb2+、Hg2+、Cu2+、Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Zn2+、Cd2+、Al3+、K+And Na+It is optional etc. in the solution system coexisted
Selecting property identifies Cu2+, strong antijamming capability.
4th, dione pyrrolo-pyrrole dyestuff stable performance of the invention, it is cheap and easy to get, it is greatly strengthen in Cu2+Detection
In practicality.
Brief description of the drawings
【Fig. 1】The hydrogen nuclear magnetic resonance spectrogram of several dione pyrrolo-pyrrole dyestuffs；
【Fig. 2】The acetonitrile solution of several dione pyrrolo-pyrrole dyestuffs is adding Cu2+Front and rear ultravioletvisible absorption light
The change of spectrum；
【Fig. 3】The block diagram that FDPP-C8 chemical probes respond to different metal ions；
【Fig. 4】FDPP-C8 acetonitrile solution (1 × 10-4Mol/L Cu is added in)2+Front and rear electron paramagnetic resonance (EPR)
Spectrogram.
Embodiment
Content for a better understanding of the present invention, the present invention is further illustrated below by specific example and legend
Technical scheme.But these embodiments are not intended to limit protection scope of the present invention.
Three kinds of typical dione pyrrolo-pyrrole Cu2+The structural formula of probe is as shown below.FDPP, FDPP-C8 and
TDPP-C8 possesses different aromatic group (thienyl and furyl) and N atoms modification group (hydrogen atom and alkyl chain).Implement
Example 1,2,3 deploys (hydrogen nuclear magnetic resonance modal data is shown in Fig. 1) by representative of these three typical dyes of figure below.
Embodiment 1
The acetonitrile solution of three kinds of representative dione pyrrolo-pyrrole dyestuffs (FDPP, FDPP-C8 and TDPP-C8) is adding
Cu2+The change of front and rear ultraviolet-visible absorption spectroscopy is as shown in Figure 1.In acetonitrile solution, FDPP, FDPP-C8 and TDPP-C8's
The UV absorption of acetonitrile solution (10 μ Μ) the expression characteristicses absworption peak at 508nm, 534nm and 543nm respectively.With Cu2+By
Gradually add, the characteristic absorption peak of three kinds of dyestuffs weakens, new absworption peak (being followed successively by 560nm, 600nm, 596nm) occur and by
It is cumulative strong.The description of test dione pyrrolo-pyrrole dyestuff can be by UV-Visible absorption spectrum to Cu2+Carry out Ratio-type
Detection.
Embodiment 2
It is as shown in Figure 3 that FDPP-C8 chemical probes respond block diagram to interfering ion.In the FDPP- that molar concentration is 10 μ Μ
In C8 acetonitrile solutions, the Ag of 10 times of equivalents is separately added into+,Pb2+,Hg2+,Cr3+,Mn2+,Fe3+,Co2+,Ni2+,Zn2+,Cd2+,Al3 +,K+,Na+With the Cu of 1 times of equivalent2+.UV absorption intensity of 14 parts of samples before and after metal ion is added at 600nm is recorded to become
Change.The contrast test illustrates the strong antijamming capability of TDPP-C8 chemical sensors and selectivity.
Embodiment 3
FDPP-C8 dyestuffs and Cu2+Front and rear electron paramagnetic resonance (EPR) spectrogram of reaction is as shown in Figure 4.It is in molar concentration
1×10-4In mol/L FDPP-C8 acetonitrile solutions, the Cu of 2 times of equivalents is added2+Afterwards, its EPR spectrogram is recorded.And with not adding Cu2+
FDPP acetonitrile solution EPR collection of illustrative plates and pure Cu2+The EPR collection of illustrative plates of acetonitrile solution proves after being compared, pyrrolopyrrole two
Ketone dyestuff and Cu2+Specific reaction can generate pyrrolo-pyrrole-dione radical cation, so as to cause optical property
Change.
Claims (8)
1. dione pyrrolo-pyrrole dyestuff is in trace Cu2+Application in detection, it is characterised in that：Pyrroles with the structure of formula 1
And pyrrole-dione dyestuff is as Cu2+Detection probe application；
Wherein,
R1And R2It is independently selected from phenyl, phenyl derivatives, thienyl, furyl or other conjugation groups；
R3And R4It is independently selected from hydrogen, alkyl, alkyloxy-ethers chain or other flexible groups.
2. dione pyrrolo-pyrrole dyestuff according to claim 1 is in trace Cu2+Application in detection, its feature exist
In：
R1And R2It is selected from thienyl or furyl；
R3And R4It is selected from hydrogen or alkyl.
3. dione pyrrolo-pyrrole dyestuff according to claim 2 is in trace Cu2+Application in detection, its feature exist
In：The alkyl is C1~C20Alkyl.
4. the dione pyrrolo-pyrrole dyestuff according to any one of claims 1 to 3 is in trace Cu2+Application in detection,
It is characterized in that：The dione pyrrolo-pyrrole dyestuff has the structure of 2~formula of formula 4：
5. the dione pyrrolo-pyrrole dyestuff according to any one of claims 1 to 3 is in trace Cu2+Application in detection,
It is characterized in that：The dione pyrrolo-pyrrole dyestuff and Cu2+Generation specific chemical reaction generation pyrrolo-pyrrole-dione
Radical cation and Cu+。
6. dione pyrrolo-pyrrole dyestuff according to claim 5 is in trace Cu2+Application in detection, its feature exist
In：The dione pyrrolo-pyrrole dyestuff by with Cu2+The front and rear ultraviolet-visible absorption spectroscopy of reaction changes to realize
Cu2+Identification.
7. dione pyrrolo-pyrrole dyestuff according to claim 6 is in trace Cu2+Application in detection, its feature exist
In：The dione pyrrolo-pyrrole dyestuff is in Ag+、Pb2+、Hg2+、Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Zn2+、Cd2+、Al3+、K+、Na+At least one of and Cu2+Selective recognition Cu in solution system coexists2+。
8. dione pyrrolo-pyrrole dyestuff according to claim 7 is in trace Cu2+Application in detection, its feature exist
In：The solution system includes acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710892485.3A CN107677659B (en) | 2017-09-27 | 2017-09-27 | Application of pyrrolopyrrole diketone dye in trace bivalent copper ion detection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710892485.3A CN107677659B (en) | 2017-09-27 | 2017-09-27 | Application of pyrrolopyrrole diketone dye in trace bivalent copper ion detection |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107677659A true CN107677659A (en) | 2018-02-09 |
| CN107677659B CN107677659B (en) | 2020-02-07 |
Family
ID=61138538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710892485.3A Active CN107677659B (en) | 2017-09-27 | 2017-09-27 | Application of pyrrolopyrrole diketone dye in trace bivalent copper ion detection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107677659B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109097027A (en) * | 2018-09-04 | 2018-12-28 | 中南大学 | Application of the dione pyrrolo-pyrrole compound/tetraphenyl ethylene class compound composite nanoparticle in hypochlorite ion detects |
| CN112516321A (en) * | 2020-12-24 | 2021-03-19 | 中南大学 | Controlled release nano-drug carrier and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1432777A1 (en) * | 2001-08-10 | 2004-06-30 | Ciba SC Holding AG | Fluorescent diketopyrrolopyrrole analogues |
| CN1871509A (en) * | 2003-10-22 | 2006-11-29 | 东洋油墨制造株式会社 | Proton acceptance type sensor, hydrogen gas sensor and acid sensor |
| CN103087083A (en) * | 2013-01-17 | 2013-05-08 | 中国科学院宁波材料技术与工程研究所 | Diketopyrrolopyrrole derivative and preparation method and application thereof |
| CN103804952A (en) * | 2014-01-23 | 2014-05-21 | 上海百艳实业有限公司 | Pyrrolopyrroledione pigment composition |
| CN104403351A (en) * | 2014-12-02 | 2015-03-11 | 中国科学院化学研究所 | Organic photosensitive dye based on symmetrical diketopyrrolopyrrole as conjugate bridge |
| CN104447764A (en) * | 2014-12-29 | 2015-03-25 | 华东理工大学 | Diketopyrrolopyrrole derivative and synthesis method thereof |
| CN104818013A (en) * | 2015-03-20 | 2015-08-05 | 中南大学 | Application of diketopyrrolopyrrole derivative in detection of Hg<2+> |
-
2017
- 2017-09-27 CN CN201710892485.3A patent/CN107677659B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1432777A1 (en) * | 2001-08-10 | 2004-06-30 | Ciba SC Holding AG | Fluorescent diketopyrrolopyrrole analogues |
| CN1541259A (en) * | 2001-08-10 | 2004-10-27 | �������⻯ѧƷ�ع�����˾ | Fluorescent diketopyrrolopyrrole analogues |
| CN1871509A (en) * | 2003-10-22 | 2006-11-29 | 东洋油墨制造株式会社 | Proton acceptance type sensor, hydrogen gas sensor and acid sensor |
| CN103087083A (en) * | 2013-01-17 | 2013-05-08 | 中国科学院宁波材料技术与工程研究所 | Diketopyrrolopyrrole derivative and preparation method and application thereof |
| CN103804952A (en) * | 2014-01-23 | 2014-05-21 | 上海百艳实业有限公司 | Pyrrolopyrroledione pigment composition |
| CN104403351A (en) * | 2014-12-02 | 2015-03-11 | 中国科学院化学研究所 | Organic photosensitive dye based on symmetrical diketopyrrolopyrrole as conjugate bridge |
| CN104447764A (en) * | 2014-12-29 | 2015-03-25 | 华东理工大学 | Diketopyrrolopyrrole derivative and synthesis method thereof |
| CN104818013A (en) * | 2015-03-20 | 2015-08-05 | 中南大学 | Application of diketopyrrolopyrrole derivative in detection of Hg<2+> |
Non-Patent Citations (3)
| Title |
|---|
| KAIXUAN NIE 等: "Thienyl diketopyrrolopyrrole as a robust sensing platform formultiple ions and its application in molecular logic system", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| MATINDER KAUR AND DONG HOON CHOI: "Dual channel receptor based on diketopyrrolopyrrole alkyne conjugate for detection of Hg2+/Cu2+ by "naked eye" and fluorescence", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| 聂凯旋 等: "基于吡咯并吡咯二酮的铜(Ⅱ)离子探针Boc-DPP的性能研究", 《中国化学会第30届学术年会-第二十七分会：光化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109097027A (en) * | 2018-09-04 | 2018-12-28 | 中南大学 | Application of the dione pyrrolo-pyrrole compound/tetraphenyl ethylene class compound composite nanoparticle in hypochlorite ion detects |
| CN112516321A (en) * | 2020-12-24 | 2021-03-19 | 中南大学 | Controlled release nano-drug carrier and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107677659B (en) | 2020-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | A multifunctional Schiff base as a fluorescence sensor for Fe3+ and Zn2+ ions, and a colorimetric sensor for Cu2+ and applications | |
| Du et al. | Fluorescent chemodosimeters using “mild” chemical events for the detection of small anions and cations in biological and environmental media | |
| AbhijnaKrishna et al. | A review on fluorimetric and colorimetric detection of metal ions by chemodosimetric approach 2013–2021 | |
| Sun et al. | A simple, reversible, colorimetric and water-soluble fluorescent chemosensor for the naked-eye detection of Cu2+ in~ 100% aqueous media and application to real samples | |
| Fang et al. | Small-molecule-based fluorescent probes for f-block metal ions: A new frontier in chemosensors | |
| CN103468247B (en) | Molecule clamp phenanthroline-benzazoles fluorescent reagent and its preparation method and application | |
| Jain et al. | A comprehensive compendium of literature of 1, 8-Naphthalimide based chemosensors from 2017 to 2021 | |
| Li et al. | A novel colorimetric and fluorescent probe based on indolium salt for detection of cyanide in 100% aqueous solution | |
| CN103012418B (en) | 1,3,4-oxadizaole structure unit-containing Rhodamine B pH fluorescence probe and applications thereof | |
| US9970878B2 (en) | Higher order structured dyes with enhanced optical features | |
| Grabchev et al. | Photophysical investigations on the sensor potential of novel, poly (propylenamine) dendrimers modified with 1, 8-naphthalimide units | |
| Pan et al. | AIE-ESIPT based colorimetric and “OFF-ON-OFF” fluorescence Schiff base sensor for visual and fluorescent determination of Cu2+ in an aqueous media | |
| Mashraqui et al. | A new internal charge transfer probe for the highly selective detection of Zn (II) by means of dual colorimetric and fluorescent turn-on responses | |
| CN107602600A (en) | The pyrroles's near-infrared pH fluorescence probes of amino substituted nitrogen heterocyclic fluorine boron two and its preparation method and purposes | |
| CN107677659A (en) | Application of the dione pyrrolo-pyrrole dyestuff in the detection of trace bivalent cupric ion | |
| Kaur | Anthraquinone appended chemosensors for fluorescence monitoring of anions and/or metal ions | |
| Chopra et al. | Fluorescent organic nanoparticles as chemosensor for nanomolar detection of Cs+ in aqueous medium | |
| Tsukamoto et al. | A Naphthalimide‐Based Cd2+ Fluorescent Probe with Carbamoylmethyl Groups Working as Chelators and PET‐Promoters under Neutral Conditions | |
| Yan et al. | A photochromic salicylaldehyde hydrazone derivative based on CN isomerization and ESIPT mechanisms and its detection of Al3+ in aqueous solution | |
| Wu et al. | A novel flavonol-based fluorescent probe for rapid detection of Hg2+ and its multi-functional applications | |
| Mahapatra et al. | Imino–phenolic–azodye appended rhodamine as a primary fluorescence “off–on” chemosensor for tin (Sn 4+) in solution and in RAW cells and the recognition of sulphide by [AR–Sn] | |
| Shen et al. | Development and application of a novel β-diketone difluoroboron-derivatized fluorescent probe for sensitively detecting H2S | |
| Zhu et al. | An EDTA promoted coordination induced disaggregation for specific Hg2+ detection | |
| Liu et al. | A new “turn-on” fluorescent sensor for highly selective sensing of H2PO4− | |
| CN101817838B (en) | Cadmium ion probe and synthesis method thereof |
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 |