CN113061088A - Asymmetric column [5] arene and preparation method and application thereof - Google Patents
Asymmetric column [5] arene and preparation method and application thereof Download PDFInfo
- Publication number
- CN113061088A CN113061088A CN202110382716.2A CN202110382716A CN113061088A CN 113061088 A CN113061088 A CN 113061088A CN 202110382716 A CN202110382716 A CN 202110382716A CN 113061088 A CN113061088 A CN 113061088A
- Authority
- CN
- China
- Prior art keywords
- arene
- column
- asymmetric
- dichloromethane
- asymmetric column
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
- C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/92—Systems containing at least three condensed rings with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an asymmetric column [5]]Aromatic hydrocarbon and a preparation method and application thereof, belonging to the technical field of macromolecular compounds. The asymmetryColumn [5]]An aromatic hydrocarbon having the formula:
asymmetric column [5] designed and synthesized by the invention]The arene P1 as a novel non-porous adaptive crystal has unique functional groups and cavity structures, can perform selective adsorption separation on dichloromethane in mixed gas of dichloromethane, trichloromethane and iodomethane, and has the advantages of selectivity and reversibility.
Description
Technical Field
The invention belongs to the technical field of high molecular compounds, and particularly relates to asymmetric column [5] arene and application thereof in selective adsorption and separation of mixed halogenated hydrocarbon.
Background
In recent years, organic materials based on supramolecular macrocyclic compound crystals are developed rapidly and applied to the fields of biomedicine, molecular recognition and the like, wherein a macrocyclic compound seems to be a non-porous material but has a cavity structure or lattice cavity which can be used by guest molecules, and the material can achieve the effect of adsorbing certain specific molecules through the interaction between the special cavity structure and a host and the guest generated by the guest, and is called non-porous adaptive crystals (NACs). The column arene is a new generation of macrocyclic main compound and is also widely applied to NACs (NACs) materials, wherein the column arene is a cyclic structure which takes hydroquinone ether and derivatives thereof as monomers and is oligomerized through methylene bridging at 2, 5-positions of the monomers, and generally has 5-10 repeating units. Compared with the traditional macrocyclic compound, the pillared arene has the characteristics of rigid structure, easy functionalization and the like, and can be subjected to host-guest complexation with a wider variety of guest molecules, so that the organic material based on the pillared arene crystal can be used as an excellent NACs material. In the research process of the column aromatic hydrocarbon, the synthesis of different functionalized column aromatic hydrocarbon structures is the focus of research of many scholars, but the asymmetric column aromatic hydrocarbon is not widely researched due to the reasons of low yield, difficult separation of isomers and the like.
Most of the column aromatics currently applied to NACs materials are known symmetric structures, such as methoxy column [5] arene or column [4] arene [1] quinone and derivatives thereof, and many reports on asymmetric column aromatics are focused on the structures and have few application researches.
Disclosure of Invention
It is an object of the present invention to design and synthesize a novel asymmetric column [5] arene.
Another object of the present invention is to provide the use of the novel asymmetric column [5] aromatics in the selective adsorption and separation of mixed halogenated hydrocarbons.
In order to achieve the purpose, the invention adopts the following technical scheme:
an asymmetric column [5] arene having the formula:
the asymmetric column [5] arene is synthesized by adopting a route shown as the following formula:
the application of the asymmetric column [5] arene in the adsorption separation of halogenated hydrocarbon.
The halogenated alkane is dichloromethane.
The asymmetric column [5] arene P1 designed and synthesized by the invention has unique functional groups and cavity structures as a novel non-porous adaptive crystal, can selectively adsorb and separate dichloromethane in mixed gas of dichloromethane, trichloromethane and iodomethane, can separate adsorbed gas under specific conditions, and has the advantages of selectivity and reversibility.
The selective adsorption of the asymmetric column [5] arene P1 on methylene chloride gas molecules is mainly due to the fact that the column arene P1 molecules can form a stable crystal structure after methylene chloride is captured, which can be seen from the single crystal structure analysis in the figure I, and the generation of a new crystal structure after adsorption is laterally proved by PXRD.
Drawings
FIG. 1 shows the single crystal structure analysis of asymmetric column [5] arene P1 after adsorbing dichloromethane.
FIG. 2 shows nuclear magnetic hydrogen spectra of asymmetric column [5] arene P1 after adsorbing a sample, wherein (a) is dichloromethane, (b) is trichloromethane, (c) is iodomethane, and (d) is a mixed gas of the three.
FIG. 3 is a powder X-ray diffraction pattern of asymmetric column [5] arene P1 after adsorbing dichloromethane.
FIG. 4 is a gas chromatogram of the gas released after adsorption of methylene chloride by asymmetric column [5] arene P1.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific examples, which should not be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. The experimental methods and reagents of the formulations not specified in the examples are in accordance with the conventional conditions in the art.
Example 1
The synthetic route of the novel asymmetric column [5] arene P1 is as follows:
the preparation process comprises the following steps:
(1) synthesis of monomer 2: hydroquinone (2.2g,0.02mol) and 3-bromopropyne (2.4g,0.02mol) were dissolved in 50mL of acetone in a 100mL round bottom flask, heated under reflux with magnetic stirring for 12h, and TCL checked for reaction progress. After the reaction was completed, the system was concentrated, and the crude product was separated by thin layer chromatography (PE: EA ═ 50:1) to obtain monomer 1 as a brown oily liquid. Monomer 1(3.0g,0.02mol) and methyl chloroacetate (4.3g,0.04mol) were weighed into a 100mL round bottom flask and dissolved in 50mL acetone, heated to reflux with magnetic stirring for 12h, and TCL checked for reaction progress. After the reaction was complete, the system was concentrated and the crude product was washed 2-3 times with 30mL to afford monomer 2 as a white solid in 56% yield.
(2) Synthesis of asymmetric column [5] arene P1: in a 100mL round bottom flask, weighing monomer 2(2.2g,0.01mol) and trioxymethylene (1.7g,0.02mol) to dissolve in 50mL dichloromethane, stirring at normal temperature for 30min, adding 1mL boron trifluoride diethyl etherate, stirring at normal temperature for 4h, and detecting the reaction progress by TCL. After the reaction, the system was concentrated, and the crude product was separated by thin layer chromatography (PE: DCM: EA ═ 10:5:1), recrystallized from ethanol, and filtered by suction to give P1 as a pale yellow solid.
P1 light yellow solid, 1%,1H NMR(400MHz,CDCl3)δ:6.91(s,5H,ArH),δ:6.88(s,5H,ArH),δ:4.59-4.58(d,10H,OCH2),δ:4.53(s,10H,OCH2),δ:3.83(s,10H,CH2),δ:3.49(s,15H,OCH3),δ:2.34-2.33(t,5H,CH).
example 2
Adsorption of halogenated hydrocarbon gas based on asymmetric column [5] arene P1 as non-porous adaptive crystal material
Weighing four groups of 50mg asymmetric column [5] arene P1 in a gas phase sampling bottle, respectively placing the four groups of samples in the atmosphere of dichloromethane, methyl iodide, trichloromethane and the mixed gas of the three in equal amount, and carrying out nuclear magnetic resonance hydrogen spectrum analysis, powder X-ray diffraction analysis and other characterizations on the four groups of samples.
By nuclear magnetic resonance hydrogen spectroscopy (1H NMR), single crystal structure analysis, and characterization means such as powder X-ray diffraction (P-XRD) on the synthesized asymmetric column [5]]And (5) characterizing the aromatic hydrocarbon.
FIG. 1 shows the single crystal structure analysis of asymmetric column [5] arene P1 after adsorbing dichloromethane, and it can be seen that dichloromethane molecules are adsorbed inside the cavity of asymmetric column [5] arene P1 through host-guest interaction, which proves that the synthesized material can adsorb and separate dichloromethane under certain conditions.
FIG. 2 is nuclear magnetic hydrogen spectrum of asymmetric column [5] arene P1 after adsorbing four groups of samples, and it can be seen that: in the atmosphere of single dichloromethane (a) and trichloromethane (b), the asymmetric column [5] arene P1 can adsorb gas molecules, in the atmosphere of iodomethane (c), the nuclear magnetic resonance hydrogen spectrum of the asymmetric column [5] arene P1 has no peak change and can not adsorb the iodomethane gas, and in the atmosphere of mixed gas of the three gases (d), the asymmetric column [5] arene P1 can selectively adsorb dichloromethane gas in the three gases.
FIG. 3 is a powder X-ray diffraction analysis of asymmetric column [5] arene P1 after adsorbing methylene chloride, showing that: after adsorbing the dichloromethane, the P-XRD peak pattern of the asymmetric column [5] arene P1 is obviously changed compared with the intensity and before adsorption, which indicates that the column arene P1 forms a new structure after adsorption.
FIG. 4 is a gas chromatograph of asymmetric column [5] arene P1 adsorbing methylene chloride followed by heating to release gas, and it can be seen that: after the adsorbed column aromatic hydrocarbon material is heated to 100 ℃, the adsorbed gas can be released from the cavity of the column aromatic hydrocarbon, and the gas chromatography analysis is carried out on the released gas, so that the content of dichloromethane can reach more than 99 percent, which shows that the selective adsorption capacity of the column aromatic hydrocarbon material is strong, and the cyclic utilization can be realized.
Example 3
Test of adsorption and separation effects of non-porous adaptive crystal material
The adsorption separation effect of the prepared material on the mixed halogenated hydrocarbon was analyzed by headspace gas chromatography, the sample after adsorption was sealed and heated in vacuum at 100 ℃ for 10 hours, and then the composition of the gas at the top of the gas-phase sampling bottle was analyzed by gas chromatography, and it was found that 99.1% of the adsorbed gas was dichloromethane. And the material can release adsorbed gas after being heated, so that cyclic utilization can be realized. Fig. 4 is a gas chromatogram of its released gas.
Claims (4)
1. An asymmetric column [5] arene having the formula:
2. the asymmetric column [5] arene of claim 1, synthesized using the route shown in the following formula:
3. use of an asymmetric column [5] arene according to claim 1 in adsorption separation of halogenated alkanes.
4. Use according to claim 3, characterized in that: the halogenated alkane is dichloromethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110382716.2A CN113061088B (en) | 2021-04-09 | 2021-04-09 | Asymmetric column [5] arene and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110382716.2A CN113061088B (en) | 2021-04-09 | 2021-04-09 | Asymmetric column [5] arene and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113061088A true CN113061088A (en) | 2021-07-02 |
| CN113061088B CN113061088B (en) | 2023-05-02 |
Family
ID=76566631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110382716.2A Active CN113061088B (en) | 2021-04-09 | 2021-04-09 | Asymmetric column [5] arene and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113061088B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114832857A (en) * | 2022-04-20 | 2022-08-02 | 南通大学 | Size selective catalyst based on column aromatic hydrocarbon and application thereof |
| CN115286524A (en) * | 2022-08-10 | 2022-11-04 | 浙江大学杭州国际科创中心 | Cyclobutylamine modified monoquinopillar [5] arene crystal material and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003851A (en) * | 2014-05-08 | 2014-08-27 | 中南大学 | Biphenyl short-chain linear polymer and preparation method thereof |
| CN104739769A (en) * | 2015-03-04 | 2015-07-01 | 王海龙 | Preparation method of liposome and product prepared by preparation method of liposome |
| WO2018061032A1 (en) * | 2016-09-30 | 2018-04-05 | Council Of Scientific & Industrial Research | Twelve-armed hexaphenylbenzene-based giant supramolecular sponge for molecular inclusion and process for preparation thereof |
| CN108341748A (en) * | 2017-01-25 | 2018-07-31 | 中国科学院理化技术研究所 | Unimolecule resin, positive photoresist and its application of the one kind based on 1,4 2 substitution column [5] arene derivatives |
| CN109053392A (en) * | 2018-08-16 | 2018-12-21 | 天津大学 | A kind of synthetic method of column [n] aromatic hydrocarbons containing a variety of functional groups |
| CN109400900A (en) * | 2018-10-30 | 2019-03-01 | 西北师范大学 | Supermolecular gel based on the assembling of column [5] aromatic hydrocarbons Subjective and Objective and its application in detection and absorption iron ion |
| CN110193344A (en) * | 2019-07-03 | 2019-09-03 | 云南民族大学 | A kind of aromatic modified zeolite adsorbent material of cation seperation column [5] and its preparation method and application |
| CN110951087A (en) * | 2019-12-10 | 2020-04-03 | 西北师范大学 | Host-guest assembled supramolecular polymer gel and preparation and application of metal thereof |
| US20200172471A1 (en) * | 2015-08-10 | 2020-06-04 | Ramot At Tel-Aviv University Ltd. | Cationic pillararenes and uses thereof |
| CN111362774A (en) * | 2020-03-03 | 2020-07-03 | 浙江大学 | Application of ethoxy column [6] arene crystal material in selective adsorption of heterocyclic compound |
-
2021
- 2021-04-09 CN CN202110382716.2A patent/CN113061088B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003851A (en) * | 2014-05-08 | 2014-08-27 | 中南大学 | Biphenyl short-chain linear polymer and preparation method thereof |
| CN104739769A (en) * | 2015-03-04 | 2015-07-01 | 王海龙 | Preparation method of liposome and product prepared by preparation method of liposome |
| US20200172471A1 (en) * | 2015-08-10 | 2020-06-04 | Ramot At Tel-Aviv University Ltd. | Cationic pillararenes and uses thereof |
| WO2018061032A1 (en) * | 2016-09-30 | 2018-04-05 | Council Of Scientific & Industrial Research | Twelve-armed hexaphenylbenzene-based giant supramolecular sponge for molecular inclusion and process for preparation thereof |
| CN108341748A (en) * | 2017-01-25 | 2018-07-31 | 中国科学院理化技术研究所 | Unimolecule resin, positive photoresist and its application of the one kind based on 1,4 2 substitution column [5] arene derivatives |
| CN109053392A (en) * | 2018-08-16 | 2018-12-21 | 天津大学 | A kind of synthetic method of column [n] aromatic hydrocarbons containing a variety of functional groups |
| CN109400900A (en) * | 2018-10-30 | 2019-03-01 | 西北师范大学 | Supermolecular gel based on the assembling of column [5] aromatic hydrocarbons Subjective and Objective and its application in detection and absorption iron ion |
| CN110193344A (en) * | 2019-07-03 | 2019-09-03 | 云南民族大学 | A kind of aromatic modified zeolite adsorbent material of cation seperation column [5] and its preparation method and application |
| CN110951087A (en) * | 2019-12-10 | 2020-04-03 | 西北师范大学 | Host-guest assembled supramolecular polymer gel and preparation and application of metal thereof |
| CN111362774A (en) * | 2020-03-03 | 2020-07-03 | 浙江大学 | Application of ethoxy column [6] arene crystal material in selective adsorption of heterocyclic compound |
Non-Patent Citations (1)
| Title |
|---|
| LU, BING ET AL.: "Rim-differentiated pillar[5]arene based nonporous adaptive crystals" * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114832857A (en) * | 2022-04-20 | 2022-08-02 | 南通大学 | Size selective catalyst based on column aromatic hydrocarbon and application thereof |
| CN114832857B (en) * | 2022-04-20 | 2023-09-19 | 南通大学 | Size selective catalyst based on column aromatic hydrocarbon and application thereof |
| CN115286524A (en) * | 2022-08-10 | 2022-11-04 | 浙江大学杭州国际科创中心 | Cyclobutylamine modified monoquinopillar [5] arene crystal material and preparation method and application thereof |
| CN115286524B (en) * | 2022-08-10 | 2023-09-01 | 浙江大学杭州国际科创中心 | Cyclobutylamine modified Shan Kunzhu [5] arene crystal material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113061088B (en) | 2023-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Malatesta et al. | Absolute rate constants for the reactions of tert-butoxyl with ethers: importance of the stereoelectronic effect | |
| CN113061088B (en) | Asymmetric column [5] arene and preparation method and application thereof | |
| Brotin et al. | Synthesis of deuterium‐labeled cryptophane‐A and investigation of Xe@ cryptophane complexation dynamics by 1D‐EXSY NMR experiments | |
| KR20080075832A (en) | Stationary phase and column using cucurbituril bonded silica gel, and separation method of taxol using the column | |
| KR20140030267A (en) | Process for the preparation of deuterated compounds containing n-alkyl groups | |
| Franck et al. | Synthesis of 1, 8-di-tert-butylnaphthalenes | |
| Jiang et al. | Templated versus non-templated synthesis of benzo-21-crown-7 and the influence of substituents on its complexing properties | |
| CN109503337B (en) | Triptycene oxygen-containing straight-chain diol functional material, preparation and application thereof | |
| CN107759475B (en) | Dehydroabietylamine derivative and preparation method and application thereof | |
| CN105461615A (en) | Preparation method of non-ionic fullerene-containing amphiphilic molecule | |
| Cooke Jr et al. | Elimination reactions. III. Hofmann elimination in cyclic compounds | |
| Klaes et al. | First synthesis, isolation and characterization of enantiomerically pure and inherently chiral resorc [4] arenes by Lewis acid cyclization of a resorcinol monoalkyl ether | |
| CN115611906B (en) | Tetra (bromoethoxy) anthracene group-containing glycoluril molecular clamp, preparation method and application thereof | |
| Harano et al. | Frontier-controlled pericyclic reactions of a powerful electron-attracting fused-ring cyclopentadienone | |
| CN111153775A (en) | Preparation method of triclosan methyl ester | |
| CN107056829B (en) | BODIPY derivative and preparation method containing uracil group | |
| CN112939751B (en) | Fluoren aromatic hydrocarbon macrocycle, preparation method thereof and application thereof in construction of functional conjugated band-shaped compound | |
| Smítalová et al. | Components of the extract from the underground parts of Laserpitium siler L. of Slovenian origin, mainly sesquiterpenic lactones | |
| CN113666928A (en) | Preparation method of novel lovaene-2N with nitrogen atoms doped on serrated edge | |
| CN115403475A (en) | Preparation method and application of diagnostic reagent for specifically detecting copper ion concentration | |
| CN113185416A (en) | Synthesis and application of novel water-soluble pillar aromatic hydrocarbon | |
| Bonaccorsi et al. | Synthesis of enantiopure sugar-decorated six-armed triptycene derivatives | |
| Soysa et al. | Pyrolysis of 1, 1, 2, 2, 2-tetramethyl-1, 2-disila-3, 6-dithiacyclohexane; Evidence for dimethylsilathione [(CH3) 2Si S] intermediates | |
| Hochmuth et al. | Determination of the rotational energy barrier of planar‐chiral cyclophanes using dynamic enantioselective gas chromatography and computer simulation | |
| Dreyer | Chemotaxonomy of the Rutaceae. VII. Alkaloids in Evodia xanthoxyloides |
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 |