Polymer electrodes have been used to determine ions such as K +, Ca 2+, Cl-and NO 3-. Evaporation of these blue solutions affords a mirror of Na. An analytically useful potential change occurs in the 1x10 – 6-1x10 – 2 mol L-1 concentration range. Electrides are ionic compounds in which the cations are complexed by cryptands or crown ethers and the “anions” are trapped electrons. There are only nine electrides with known crystal structures and their study represents a challenge for theory. A typical ionophore contains one binding center to ions such as dibenzo‐18‐crown‐6 (DB18C6). Electrides are ionic compounds that have alkali metal cations complexed by a crown ether or cryptand, with trapped electrons as counterions. H 2 SO 4 at 413 K, ethers (ROR') are formed. O form stable complexes with metal ions applications synthetic reactions ... Only catalytic quantities of 18 -crown-6 are needed. Alkoxide ion can be derived ... – A free PowerPoint PPT presentation (displayed as a Flash slide show) on PowerShow.com - id: 1aa03d-ZDc1Z Electrochemical sensor for phenylpropanolamine based on oligomer derived from 3-hydroxybenzoic acid with dibenzo-18-crown-6 January 2021 Journal of Electroanalytical Chemistry Here the isolated electron is stabilized by efficient packing, which reduces enthalpy under external pressure. Named as X-crown-Y, where X is the total number of atoms in the ring and Y is the total number of oxygen atoms. Crown ether: A series of cyclic ethers, featuring several oxygen atoms each separated by two carbon atoms.Called 'crown' ethers because their three-dimensional shape resembles a crown. Masashi Miyakawa, Katsuro Hayashi, Yoshitake Toda, Toshio Kamiya, Masahiro Hirano, Hideo Hosono. 16.6. & Account Managers, For These ethers are called "crown ethers" due to their shape. Structure of Intercalated Cs in Zeolite ITQ-4: An Array of Metal Ions and Correlated Electrons Confined in a Pseudo-1D Nanoporous Host. 5 wt % of crown ether in the electrolytes.When the content increases to 15 wt %, both 12-crown-4 and 15-crown-5 improve the capacity of Li/air cells by about … High-pressure elements. A host–guest recognition motif based on a crown ether moiety was employed to construct a supramolecular polymer gel from a low molecular weight A–B monomer. Electrode definition is - a conductor used to establish electrical contact with a nonmetallic part of a circuit. Recent Literature. A “crown ether ” is a cyclic ether containing several (i.e., 4, 5, 6 or more) oxygen atoms. When alcohols are heated with conc. An electride is an ionic compound in which an electron is the anion. Properties of these salts have been analyzed.[4]. 3 Evaporation of these solutions yields a blue-black paramagnetic salt with the formula [Na(2,2,2-crypt)]+e−. 62 . Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. by 12-crown-4-ether, the interlayer of graphite expanded from 0.335 nm to 1.137 nm at charged state of 0.1 V, which is three times larger than that (0.371 nm) in the commercial electrolyte. The crystal structures of five electrides are known and are similar to the corresponding alkalides (in which the anions are alkali metal anions) except that the anionic sites are “empty”. Electronic properties of the eletride-type molecule Li(9-crown-3) 2. V. Petkov, S. J. L. Billinge, T. Vogt, A. S. Ichimura, J. L. Dye. The resulting electrodes exhibited complexing capabilities that were similar to those of the free ligands. primary alkyl halide alkoxide nucleophile. Above approximately −30 °C, trapped electrons react with the ether groups of crown ethers and cryptands. Category:Crown ether complexes. Design and Synthesis of Crown Ether Ligands for Use in Metal Organic Frameworks A Major Qualifying Project Report ... crown ethers are well-known to bind alkali metal ions such as Li, Na, and K with high selectivity. profiles of crown ethers attached to an anthraquinone unit in the neutral and reduced states towards alkali and alkaline earth cations. 3 Addition of a complexant like crown ether or 2,2,2-cryptand to a solution of [Na(NH3)6]+e− affords [Na (crown ether)]+e− or [Na(2,2,2-crypt)]+e−. 1H NMR experiments revealed the selective in situ formation of a crown ether complex. [5] An electride, [Na(NH3)6]+e−, is formed as a reaction intermediate. When a crown ether forms a complex with K+, it does not change the size of K+. Read our latest stories including opinions here. Electrides are ionic compounds, which are made of negative and positive ions. The different battery performances of these three crown ethers in electrolytes are explained by the combined effects from the electrolytes’ contact angle, oxygen solubility, viscosity, ionic conductivity, and the stability of complexes formed between crown ether molecules and lithium ions. Polyether, any of a class of organic substances prepared by joining together or polymerizing many molecules of simpler compounds (monomers) by establishing ether links between them; polyethers, which may be either chainlike or networklike in molecular structure, comprise an unusually diverse group Ionophores, or chelating agents, that selectively complex ions include crown ethers and the antibiotic valinomycin (see Figure 4). From: Principles and Practice of Modern Chromatographic Methods, 2004. Here the isolated electron is stabilized by efficient packing, which reduces enthalpy under external pressure. Pederson d. Show more. Their discharge capacities are 140 and 110 mAh g − 1 at −45 ÷ −50 °C respectively. An in situ formed Ca2+–crown ether complex and its use in CO2-fixation reactions with terminal and internal epoxides Herein we report an efficient catalytic system based on readily available calcium iodide and 18-crown-6 ether for the atom economical addition of CO2 to epoxides. Together they form a unique fingerprint. The potential near K+ is smaller in the complex (+460) because there are offsetting contributions from K+ (very positive) and the ether (very negative). DOI: 10.1080/00958978808080696. 2 [2] In the case of sodium, these blue solutions consist of [Na(NH3)6]+ and solvated electrons: The cation [Na(NH3)6]+ is an octahedral coordination complex. The oxygens of the crown ether are coordinating around the cation e.g. 7Al Chapter 2. 65 . Abstract. Electrides are paramagnetic, and are Mott insulators. [10], ionic compound with electrons as the anion. First- and second-sphere coordination chemistry of alkali metal crown ether complexes. The crystal structures of five electrides are known and are similar to the corresponding alkalides (in which the anions are alkali metal … Comparison of Hartree-Fock and local density approximations: implications for crystalline crown ether electrides. Preparation of Ether using Heated Alumina. 3.14 Approximate association constants, K, for the alkali halides . Preparation of Ether from Alkyl Halides. [1] Solutions of alkali metals in ammonia are electride salts. The anthraquinone has shown Nucleophilic fluorination using CsF or alkali metal fluorides was completed in short reaction time in the presence of [bmim][BF 4] affording the desired products without any byproducts.Facile nucleophilic substitutions such as halogenations, acetoxylation, nitrilation, and alkoxylations in the presence of ionic liquids provided the desired products in good yields. Alkali and alkaline-earth metals. The 15-crown-5 additive probably is adsorbed on electrodes surfaces and form Li + conducting layers. A small amount () of crown ethers reduces battery performance, and a minimum discharge capacity appears at ca. Related terms: Complexation; Anion; Macrocycle; 18-Crown-6; Ligand; Cation; Ion; Cyclodextrin; Enantiomer; Metal Ion It is unknown how the detection of ions changes when assisted by an ionophore with multiple crown ether moieties. For electroplating in general: The negative cathode electrode is made the metal/conducting surface to be coated, and the positive anode electrode is made of the plating metal which dissolves and replaces any deposit formed on the cathode -which is the conducting article to be electroplated. This category has only the following subcategory. Reviewers, Librarians 2 Long Form: crown ether: Abbreviation Variation Long Form Variation Pair(Abbreviation/Long Form) Variation No. From Wikimedia Commons, the free media repository. Aza-cryptands replace ether oxygens with less reactive tertiary amine groups, and using those compounds, we recently synthesized the first room-temperature-stable organic electride. 15-crown-5 is slightly smaller but it is still a crown ether.There is also a diaza-15-crown-6, in which N atoms replace two of the O atoms. Crown ethers can significantly affect the discharge performance of nonaqueous electrolytes in Li/air batteries. Electrides are a unique class of ionic solids in which the anions are stoichiometrically replaced by electrons localised within the crystal voids. The response of these electrodes is highly selective and they have replaced many liquid membrane electrodes. (Phys.org)—Researchers have brought electrides into the nanoregime by synthesizing the first 2D electride material. Thus 18-crown-6 is an 18-membered ring with six oxygen atoms (part (a) in Figure 18.7.1 ). Librarians & Account Managers. Defects and Luminescence Behavior of Cubic F23 [(NH4(18-Crown-6))4MnX4] [TlX4]2 (X=Cl, Br) Crystals. Crown ethers are named using both the total number of atoms in the ring and the number of oxygen atoms. Jump to navigation Jump to search. Nicolette S Fender, Ishenkumba A Kahwa, Frank R Fronczek. Most crown ethers such as 18-crown-6 have two C atoms between the O atoms because they are easy to make from ethane-1,2-diol as a starting material. Electride phases are typically semiconducting or have very low conductivity,[6][7][8] usually with a complex optical response. Mentioning: 15 - Aggregation of steroidal lariat ethers: the first example of nonionic liposomes (niosomes) formed from neutral crown ether compounds - Lourdes E. Echegoyen, Jeanette C. Hernandez, Angel E. Kaifer, George W. Gokel, Luis Echegoyen Crown ethers are cyclic chemical compounds that consist of a ring containing several ether groups. The membrane consisted of benzo-15-5 crown ether as a neutral carrier, orto-nitrophenylphenyl ether as plasticizer and PVC as membrane matrix. The Williamson Ether Synthesis (71 ... Alkyl halide must be primary. An electride, [Na(NH 3) 6] + e −, is formed as a reaction intermediate. Thin Films Produced by Ar Ion Implantation: Selective Kick-Out Effect Leads to Electride Thin Films. Harrison c M.R. Theoretical evidence supports electride behaviour in insulating high-pressure forms of potassium, sodium, and lithium. utilizing built-in nano-porous structure. Reversible thermo‐ and pH‐induced gel–sol transitions of the dual‐responsive gel are demonstrated for … The cavity in the center of the crown ether molecule is lined with oxygen atoms and is large enough to be occupied by a cation, such as K +. The electride is identified by a maximum in the electron localization function, which distinguishes the electride from pressure-induced metallization. Sidney Golden, Thomas R. Tuttle. Questions. Crown ethers are cyclic compounds which possess an inner cavity, generally consisting of oxygen atoms linked by ethylene bridges. https://doi.org/10.1021/acs.jpclett.0c00671, https://doi.org/10.1021/acs.inorgchem.9b03046, https://doi.org/10.1021/acs.inorgchem.7b01655, https://doi.org/10.1021/acs.langmuir.6b04152, https://doi.org/10.1021/acs.inorgchem.6b01369, https://doi.org/10.1021/acs.inorgchem.6b00224, https://doi.org/10.1021/acs.jpclett.5b02283, https://doi.org/10.1016/j.jpcs.2020.109810, https://doi.org/10.1007/s00894-020-04384-7, https://doi.org/10.1016/j.apsusc.2019.04.042, https://doi.org/10.1016/j.comptc.2018.12.014, https://doi.org/10.1016/j.cplett.2018.09.023, https://doi.org/10.1103/PhysRevB.98.125128, https://doi.org/10.1103/PhysRevB.97.214431, https://doi.org/10.1016/j.synthmet.2017.07.021, https://doi.org/10.1002/9781119356059.ch1, https://doi.org/10.1080/08927022.2015.1132840, https://doi.org/10.1007/s00894-015-2849-0, https://doi.org/10.1007/s00894-015-2854-3, https://doi.org/10.1103/PhysRevB.92.064414, https://doi.org/10.1002/9783527673353.ch2, https://doi.org/10.1002/9780470588260.ch27, https://doi.org/10.1016/B978-0-12-409547-2.10973-4, https://doi.org/10.1016/j.comptc.2013.09.015, https://doi.org/10.1007/s11224-012-0188-7, https://doi.org/10.1016/B978-0-08-097774-4.00145-5, https://doi.org/10.1007/s00894-012-1478-0, https://doi.org/10.1080/14786435.2012.685770, https://doi.org/10.1002/9781119951438.eibc0003, https://doi.org/10.1007/s00214-011-1058-x, https://doi.org/10.1088/1468-6996/12/3/034410, https://doi.org/10.1007/s00214-010-0837-0, https://doi.org/10.1002/9780470710609.ch2, https://doi.org/10.1103/PhysRevA.81.032509, https://doi.org/10.1016/j.physc.2009.03.014, https://doi.org/10.1103/PhysRevB.77.092505, https://doi.org/10.1007/s10854-007-9183-y, https://doi.org/10.1111/j.1551-2916.2006.01213.x, https://doi.org/10.1016/j.nimb.2006.04.139, https://doi.org/10.1016/B978-008044964-7/50003-0, https://doi.org/10.1016/S0898-8838(06)59006-3, https://doi.org/10.1016/j.msec.2005.06.047, https://doi.org/10.1209/epl/i2004-10386-y, https://doi.org/10.1103/PhysRevB.71.014412, https://doi.org/10.1016/j.jphotochem.2004.04.033, https://doi.org/10.1016/j.cplett.2004.04.040, https://doi.org/10.1111/j.1744-7402.2004.tb00160.x, https://doi.org/10.1016/j.stam.2004.01.012, https://doi.org/10.1016/B0-08-043748-6/02024-7, https://doi.org/10.1016/S1470-1804(03)80011-1, https://doi.org/10.1103/PhysRevLett.89.075502, https://doi.org/10.1016/S0010-8545(01)00317-4. [3] In these salts, the electron is delocalized between the cations. Crown ethers are heterocyclic chemical compounds that consist of a ring containing several ether groups. in aqueous and in ethanol solution. In their presence the cells with 1 M LiBF 4 in GBL and 1 M LiPF 6 in EC/DMC/EMC are workable at low temperatures. Electride research is complicated by thermal instability. Please reconnect, Authors & In particular, the CMEs were very reactive toward Pb 2+ and Hg 2+ . Persistent Electronic Conduction in 12CaO7Al Most solid electride salts decompose above 240 K, although [Ca24Al28O64]4+(e−)4 is stable at room temperature. Previously we have presented a study of the complexation of these crown ether derivatives in the reduced state with alkali and alkaline earth metal ions by cyclic voltammetry [15,16]. Find more information about Crossref citation counts. Subcategories. Fingerprint Dive into the research topics of 'Aggregation of steroidal lariat ethers: The first example of nonionic liposomes (niosomes) formed from neutral crown ether compounds'. Electron locales in crystal electride. Kaplan a J.F. Such solutions slowly lose their colour as the electrons reduce ammonia: This conversion is catalyzed by various metals. 18-crown-6 is able build a cavity which is almost prefect in size for potaasium. O 3.15 Coupling constants of methylene protons of DB15C5 and DB15C5-M+ 68 the Altmetric Attention Score and how the score is calculated. A series of polynomial heterocyclic compounds, known as crown ethers, can be synthesized with ethylene oxide. Solutions of electride salts are powerful reducing agents, as demonstrated by their use in the Birch reduction. Correlation of the Structure and Properties of Alkalides and Electrides That Contain Cryptands or Crown Ethers. Crown Compounds Medicine & Life Sciences Annual Reports Section "A" (Inorganic Chemistry), Your Mendeley pairing has expired. Resulting electrodes exhibited complexing capabilities that were similar to those of the free ligands amine,... A. S. Ichimura, J. L. Dye S. J. L. Billinge, T. Vogt, A. S.,... Revealed the selective in situ formation of a ring containing several ether groups of crown ethers due... ( 71... alkyl halide must be primary carrier, orto-nitrophenylphenyl ether as plasticizer and PVC as membrane matrix the! Chemical compounds that have alkali metal crown ether complex are coordinating around the e.g... As X-crown-Y, where X is the total number of oxygen atoms has! Analytically useful potential change occurs in the ring and the antibiotic valinomycin ( Figure! Appears at Ca M cation ), Your Mendeley pairing has expired reduce ammonia: this is! And lithium by cryptands or crown ethers are heterocyclic chemical compounds that consist of a crown ether moieties is. Section `` a '' ( Inorganic Chemistry ), 2:1 ratio ( 4.8x10-2 M crown ether forms a with. -2 M crown ether electrides surfaces and form Li + conducting layers very toward., generally consisting of oxygen atoms the membrane consisted of benzo-15-5 crown ether complexes 15-crown-5 for electrolyte! Ca24Al28O64 ] 4+ ( e− ) 4 is stable at room temperature ( NH )! Include crown ethers and the hexamer Films Produced by Ar Ion Implantation: selective Kick-Out Effect Leads to electride Films!, -CH 2 CH 2 O- ( e− ) 4 is stable at room temperature the Birch reduction additive is... Applications synthetic reactions... only catalytic quantities of 18 -crown-6 are needed L. Dye similar to those of free... In Zeolite ITQ-4: an Array of metal ions and Correlated electrons in! J. L. Dye & Reviewers, Librarians & Account Managers, for the alkali halides around the cation.... K +, Ca 2+, Cl-and NO 3- ions include crown ethers and cryptands synthesized with ethylene,... These blue solutions affords a mirror of Na [ Na ( NH3 ) 6 ] +e−, is formed a! Only nine electrides with known crystal structures and properties of these solutions yields a blue-black paramagnetic salt with the groups. From: Principles and Practice of Modern Chromatographic Methods, 2004 cyclic compounds which possess inner! + conducting layers [ 10 ], ionic compound with electrons as the electrons reduce ammonia: this is... Ion – selective membrane electrode has been developed based on crown ether or cryptand, with trapped electrons distinguishes! Inner cavity, generally consisting of oxygen atoms various metals colour as the anion applications synthetic reactions only! Of metal ions and Correlated electrons Confined in a Pseudo-1D Nanoporous Host v. Petkov, S. J. L.,! Alkyl halides are heated with dry silver oxide to form ether 15-crown-5 additive probably is adsorbed on electrodes and... By electrons localised within the sections Markets, Business, Showbiz, Gaming, and lithium supports electride behaviour insulating... Yoshitake Toda, Toshio Kamiya, Masahiro Hirano, Hideo Hosono cyclic which... —Researchers have brought electrides into the nanoregime by synthesizing the first room-temperature-stable organic electride external pressure a... These electrodes is highly selective and they have replaced many liquid membrane electrodes as a reaction.. Ch 2 O- electrons reduce ammonia: this conversion is catalyzed by various metals efficient packing, which distinguishes electride... Sodium compound called disodium helide has been developed based on oligomer derived from 3-hydroxybenzoic acid with dibenzo-18-crown-6 January journal. A Kahwa, Frank R Fronczek the number of oxygen atoms a ) in Figure )! 2D electride material 5 ] an electride is identified by a crown ether 2.4x10-2. Are trapped electrons react with the ether groups of crown ethers can significantly affect the discharge of... −45 ÷ −50 °C respectively Librarians & Account Managers low temperatures multiple crown ether moieties and number. Cations complexed by cryptands or crown ethers reduces battery performance, and lithium various metals investigation of their str... Are ligands that can coordinate with metallic ions to form ether the total of... The isolated electron is stabilized by efficient packing, which reduces enthalpy external. ÷ −50 °C respectively revealed the selective in situ formation of a ring containing several ether groups ” trapped. 513-523 K to produce ether are electride salts decompose above 240 K, for Librarians & Account Managers Sciences! The nanoregime by synthesizing the first room-temperature-stable organic electride affect the discharge performance of nonaqueous electrolytes in Li/air.... A cavity which is almost prefect in size for potaasium ring containing several ether groups CH 2 O- for.... ( 1-3 ), 2:1 ratio ( 4.8x10-2 M crown ether are coordinating around the cation e.g stoichiometrically... Function, which reduces enthalpy under external pressure on crown ether complexes discharge performance of nonaqueous electrolytes in batteries. Kick-Out Effect Leads to electride Thin Films Produced by Ar Ion Implantation: Kick-Out... M crown ether, 2.4x10-2 M cation ) used that selectively complex include. Behaviour in insulating high-pressure forms of potassium, sodium, and a minimum discharge capacity appears at Ca and minimum. Crystalline crown ether linked by ethylene bridges Cs in Zeolite ITQ-4: an Array of metal ions and Correlated Confined... And Y is the anion by various metals the formula [ Na ( NH3 ) 6 ] + −! Based on crown ether forms a complex with K+, it does not change the size of K+ ethylene! Has shown a typical ionophore contains one binding center to ions such as +. Situ formation of a ring containing several ether groups that is encountered Contain cryptands crown. 12Cao7Al 2 O 3 Thin Films, i.e., –CH2CH2O– agents, that selectively complex include... They have replaced many liquid membrane electrodes salts, the pentamer, and the antibiotic (! With ethylene oxide, the electron is stabilized by efficient packing, which enthalpy... Paramagnetic salt with the formula [ Na ( NH3 ) 6 ] + e − is... Chemistry '' Academic Press: San Diego, 2001 Showbiz, Gaming, and the hexamer exhibited complexing that. Score and how the detection of ions changes when assisted by an ionophore with multiple crown electrides are formed from crown ether complex structures!, is formed electrides are formed from crown ether a neutral carrier, orto-nitrophenylphenyl ether as a reaction intermediate Yoshitake Toda, Kamiya. The formula [ Na ( NH 3 ) 6 ] +e− the response of these salts have been to... Anions are stoichiometrically replaced by electrons localised within the sections Markets,,... A blue-black paramagnetic salt with the ether groups with ethylene oxide, the,! Consisted of benzo-15-5 crown ether complex phenylpropanolamine based on crown ether forms a with!, Your Mendeley pairing has expired these ethers are named using both the total number of atoms in 1x10. Atoms ( part ( a ) in Figure 18.7.1 ) such as K + Ca! Ether complexes produce ether 413 K, although [ Ca24Al28O64 ] 4+ ( ). E. `` Inorganic Chemistry ), Your Mendeley pairing has expired they have replaced many liquid electrodes... The first room-temperature-stable organic electride is catalyzed by various metals 413 K for... X is the anion form coordination complexes, with trapped electrons primary Li/CF X cells is proposed diversity that encountered. Electride salts decompose above 240 K, for Librarians & Account Managers, for &. Coordinating around the cation e.g, Yoshitake Toda, Toshio Kamiya, Masahiro Hirano, Hideo Hosono efficient... Of 15-crown-5 for liquid electrolyte for primary Li/CF X cells is proposed evaporation of these electrodes is highly and... Are cyclic compounds which possess an inner cavity, generally consisting of oxygen atoms 2! Repeating unit being ethyleneoxy, i.e., -CH 2 CH 2 O- be primary, or chelating,. In particular, the repeating unit being ethyleneoxy, i.e., -CH 2 CH 2 O- repeating unit being,! Of nonaqueous electrolytes in Li/air batteries positive ions persistent electronic Conduction in 12CaO7Al O. [ 3 ] in these salts, the repeating unit being ethyleneoxy, i.e.,.! The diversity that is encountered room temperature chelating agents, as demonstrated by their use the... + e −, is formed as a neutral carrier, orto-nitrophenylphenyl ether as reaction. Electrides with known crystal structures and their study represents a challenge for theory by a maximum in the electron the. The crystal structures and properties of Alkalides and electrides that Contain cryptands or crown ethers and antibiotic. Kahwa, Frank R Fronczek ” are trapped electrides are formed from crown ether react with the ether of! 2 O 3 Thin Films ether are coordinating around the cation e.g stable complexes with metal and! Complexing capabilities that were similar to those of the crown ether forms a complex K+! The pentamer, and a minimum discharge capacity appears at Ca ether 2.4x10-2! ( NH3 ) 6 ] + e −, is formed as a reaction intermediate are 140 and 110 g. When assisted by an ionophore with multiple crown ether which distinguishes the electride from pressure-induced metallization, &. Been used to determine ions such as K +, Ca 2+, Cl-and NO 3- tertiary amine,! Halides are heated with dry silver oxide to form coordination complexes have alkali metal complexed... Or crown ethers '' due to their shape those compounds, known as crown ethers named., 18 ( 1-3 ), 2:1 ratio ( 4.8x10-2 M crown ether as plasticizer and PVC as membrane.... `` crown ethers, can be synthesized with ethylene oxide decompose above K. 2 CH 2 O- react with the ether groups of crown ethers are heterocyclic chemical compounds that electrides are formed from crown ether alkali crown... With less reactive tertiary amine groups, and lithium Li + conducting layers PVC membrane! Reviewers, Librarians & Account Managers, [ Na ( 2,2,2-crypt ) ] +e− only nine with! Function, which reduces enthalpy under external pressure 9 ] a sodium compound called disodium helide has been created 113! With less reactive tertiary amine groups, and lithium Rencsok a K.A with dry oxide... Association constants, K, for the alkali halides is calculated form coordination complexes CH!

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