Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic: The Strategy for Utilization in Water Treatment and Warnings on Metal Leaching

A chromate of copper and cobalt (Φy) was synthesized and characterized. Φy activated peroxymonosulfate (PMS) to degrade ciprofloxacin (CIP) in water. The Φy/PMS combination showed a high degrading capability toward CIP (~100% elimination in 15 min). However, Φy leached cobalt (1.6 mg L−1), limiting...

Full description

Autores:
Serna Galvis, Efraím Adolfo
Mendoza Merlano, Carlos Javier
Torres Palma, Ricardo Antonio
Echavarría Isaza, Adriana
Hoyos Ayala, Dora Ángela
Tipo de recurso:
Article of investigation
Fecha de publicación:
2023
Institución:
Universidad de Antioquia
Repositorio:
Repositorio UdeA
Idioma:
eng
OAI Identifier:
oai:bibliotecadigital.udea.edu.co:10495/46077
Acceso en línea:
https://hdl.handle.net/10495/46077
Palabra clave:
Scanning electron microscopes
Oxidación
Oxidation
Antibacterianos - farmacología
Anti-Bacterial Agents - pharmacology
Ciprofloxacina - farmacología
Ciprofloxacin - pharmacology
Cobalt
Cobre
Copper
Peróxidos
Peroxides
Contaminantes Químicos del Agua - análisis
Water Pollutants, Chemical - analysis
Water treatment
Tratamiento del agua
Scanning electron microscopy
Microscopía electrónica de barrido
Metals
Metal
Chromate of copper and cobalt
http://aims.fao.org/aos/agrovoc/c_ef195799
http://aims.fao.org/aos/agrovoc/c_a87b3af2
http://aims.fao.org/aos/agrovoc/c_29036
http://id.loc.gov/authorities/subjects/sh85117990
https://id.nlm.nih.gov/mesh/D000900
https://id.nlm.nih.gov/mesh/D002939
https://id.nlm.nih.gov/mesh/D003035
https://id.nlm.nih.gov/mesh/D003300
https://id.nlm.nih.gov/mesh/D010545
https://id.nlm.nih.gov/mesh/D014874
ODS 6: Agua limpia y saneamiento. Garantizar la disponibilidad y la gestión sostenible del agua y el saneamiento para todos
Rights
openAccess
License
http://creativecommons.org/licenses/by/4.0/
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dc.title.eng.fl_str_mv Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic: The Strategy for Utilization in Water Treatment and Warnings on Metal Leaching
title Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic: The Strategy for Utilization in Water Treatment and Warnings on Metal Leaching
spellingShingle Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic: The Strategy for Utilization in Water Treatment and Warnings on Metal Leaching
Scanning electron microscopes
Oxidación
Oxidation
Antibacterianos - farmacología
Anti-Bacterial Agents - pharmacology
Ciprofloxacina - farmacología
Ciprofloxacin - pharmacology
Cobalt
Cobre
Copper
Peróxidos
Peroxides
Contaminantes Químicos del Agua - análisis
Water Pollutants, Chemical - analysis
Water treatment
Tratamiento del agua
Scanning electron microscopy
Microscopía electrónica de barrido
Metals
Metal
Chromate of copper and cobalt
http://aims.fao.org/aos/agrovoc/c_ef195799
http://aims.fao.org/aos/agrovoc/c_a87b3af2
http://aims.fao.org/aos/agrovoc/c_29036
http://id.loc.gov/authorities/subjects/sh85117990
https://id.nlm.nih.gov/mesh/D000900
https://id.nlm.nih.gov/mesh/D002939
https://id.nlm.nih.gov/mesh/D003035
https://id.nlm.nih.gov/mesh/D003300
https://id.nlm.nih.gov/mesh/D010545
https://id.nlm.nih.gov/mesh/D014874
ODS 6: Agua limpia y saneamiento. Garantizar la disponibilidad y la gestión sostenible del agua y el saneamiento para todos
title_short Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic: The Strategy for Utilization in Water Treatment and Warnings on Metal Leaching
title_full Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic: The Strategy for Utilization in Water Treatment and Warnings on Metal Leaching
title_fullStr Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic: The Strategy for Utilization in Water Treatment and Warnings on Metal Leaching
title_full_unstemmed Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic: The Strategy for Utilization in Water Treatment and Warnings on Metal Leaching
title_sort Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic: The Strategy for Utilization in Water Treatment and Warnings on Metal Leaching
dc.creator.fl_str_mv Serna Galvis, Efraím Adolfo
Mendoza Merlano, Carlos Javier
Torres Palma, Ricardo Antonio
Echavarría Isaza, Adriana
Hoyos Ayala, Dora Ángela
dc.contributor.author.none.fl_str_mv Serna Galvis, Efraím Adolfo
Mendoza Merlano, Carlos Javier
Torres Palma, Ricardo Antonio
Echavarría Isaza, Adriana
Hoyos Ayala, Dora Ángela
dc.contributor.researchgroup.none.fl_str_mv Catalizadores y Adsorbentes
Grupo de Investigación en Remediación Ambiental y Biocatálisis
Grupo de Ingeniería y Gestión Ambiental (GIGA)
dc.subject.lcsh.none.fl_str_mv Scanning electron microscopes
topic Scanning electron microscopes
Oxidación
Oxidation
Antibacterianos - farmacología
Anti-Bacterial Agents - pharmacology
Ciprofloxacina - farmacología
Ciprofloxacin - pharmacology
Cobalt
Cobre
Copper
Peróxidos
Peroxides
Contaminantes Químicos del Agua - análisis
Water Pollutants, Chemical - analysis
Water treatment
Tratamiento del agua
Scanning electron microscopy
Microscopía electrónica de barrido
Metals
Metal
Chromate of copper and cobalt
http://aims.fao.org/aos/agrovoc/c_ef195799
http://aims.fao.org/aos/agrovoc/c_a87b3af2
http://aims.fao.org/aos/agrovoc/c_29036
http://id.loc.gov/authorities/subjects/sh85117990
https://id.nlm.nih.gov/mesh/D000900
https://id.nlm.nih.gov/mesh/D002939
https://id.nlm.nih.gov/mesh/D003035
https://id.nlm.nih.gov/mesh/D003300
https://id.nlm.nih.gov/mesh/D010545
https://id.nlm.nih.gov/mesh/D014874
ODS 6: Agua limpia y saneamiento. Garantizar la disponibilidad y la gestión sostenible del agua y el saneamiento para todos
dc.subject.decs.none.fl_str_mv Oxidación
Oxidation
Antibacterianos - farmacología
Anti-Bacterial Agents - pharmacology
Ciprofloxacina - farmacología
Ciprofloxacin - pharmacology
Cobalt
Cobre
Copper
Peróxidos
Peroxides
Contaminantes Químicos del Agua - análisis
Water Pollutants, Chemical - analysis
dc.subject.agrovoc.none.fl_str_mv Water treatment
Tratamiento del agua
Scanning electron microscopy
Microscopía electrónica de barrido
Metals
Metal
dc.subject.proposal.eng.fl_str_mv Chromate of copper and cobalt
dc.subject.agrovocuri.none.fl_str_mv http://aims.fao.org/aos/agrovoc/c_ef195799
http://aims.fao.org/aos/agrovoc/c_a87b3af2
http://aims.fao.org/aos/agrovoc/c_29036
dc.subject.lcshuri.none.fl_str_mv http://id.loc.gov/authorities/subjects/sh85117990
dc.subject.meshuri.none.fl_str_mv https://id.nlm.nih.gov/mesh/D000900
https://id.nlm.nih.gov/mesh/D002939
https://id.nlm.nih.gov/mesh/D003035
https://id.nlm.nih.gov/mesh/D003300
https://id.nlm.nih.gov/mesh/D010545
https://id.nlm.nih.gov/mesh/D014874
dc.subject.ods.none.fl_str_mv ODS 6: Agua limpia y saneamiento. Garantizar la disponibilidad y la gestión sostenible del agua y el saneamiento para todos
description A chromate of copper and cobalt (Φy) was synthesized and characterized. Φy activated peroxymonosulfate (PMS) to degrade ciprofloxacin (CIP) in water. The Φy/PMS combination showed a high degrading capability toward CIP (~100% elimination in 15 min). However, Φy leached cobalt (1.6 mg L−1), limiting its use for water treatment. To avoid leaching, Φy was calcinated, forming a mixed metal oxide (MMO). In the combination of MMO/PMS, no metals leached, the CIP adsorption was low (<20%), and the action of SO4•− dominated, leading to a synergistic effect on pollutant elimination (>95% after 15 min of treatment). MMO/PMS promoted the opening and oxidation of the piperazyl ring, plus the hydroxylation of the quinolone moiety on CIP, which potentially decreased the biological activity. After three reuse cycles, the MMO still presented with a high activation of PMS toward CIP degradation (90% in 15 min of action). Additionally, the CIP degradation by the MMO/PMS system in simulated hospital wastewater was close to that obtained in distilled water. This work provides relevant information on the stability of Co-, Cu-, and Cr-based materials under interaction with PMS and the strategies to obtain a proper catalyst to degrade CIP.
publishDate 2023
dc.date.issued.none.fl_str_mv 2023
dc.date.accessioned.none.fl_str_mv 2025-05-23T17:19:06Z
dc.type.none.fl_str_mv Artículo de investigación
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dc.identifier.citation.none.fl_str_mv Serna-Galvis, E.A.; Mendoza-Merlano, C.; Torres-Palma, R.A.; Echavarría-Isaza, A.; Hoyos-Ayala, D.A. Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic—The Strategy for Utilization inWater Treatment and Warnings on Metal Leaching. Molecules 2023, 28, 4536. https://doi.org/10.3390/molecules28114536
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/10495/46077
dc.identifier.doi.none.fl_str_mv 10.3390/molecules28114536
dc.identifier.eissn.none.fl_str_mv 1420-3049
identifier_str_mv Serna-Galvis, E.A.; Mendoza-Merlano, C.; Torres-Palma, R.A.; Echavarría-Isaza, A.; Hoyos-Ayala, D.A. Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic—The Strategy for Utilization inWater Treatment and Warnings on Metal Leaching. Molecules 2023, 28, 4536. https://doi.org/10.3390/molecules28114536
10.3390/molecules28114536
1420-3049
url https://hdl.handle.net/10495/46077
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dc.relation.citationvolume.none.fl_str_mv 28
dc.relation.ispartofjournal.none.fl_str_mv Molecules
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spelling Serna Galvis, Efraím AdolfoMendoza Merlano, Carlos JavierTorres Palma, Ricardo AntonioEchavarría Isaza, AdrianaHoyos Ayala, Dora ÁngelaCatalizadores y AdsorbentesGrupo de Investigación en Remediación Ambiental y BiocatálisisGrupo de Ingeniería y Gestión Ambiental (GIGA)2025-05-23T17:19:06Z2023Serna-Galvis, E.A.; Mendoza-Merlano, C.; Torres-Palma, R.A.; Echavarría-Isaza, A.; Hoyos-Ayala, D.A. Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic—The Strategy for Utilization inWater Treatment and Warnings on Metal Leaching. Molecules 2023, 28, 4536. https://doi.org/10.3390/molecules28114536https://hdl.handle.net/10495/4607710.3390/molecules281145361420-3049A chromate of copper and cobalt (Φy) was synthesized and characterized. Φy activated peroxymonosulfate (PMS) to degrade ciprofloxacin (CIP) in water. The Φy/PMS combination showed a high degrading capability toward CIP (~100% elimination in 15 min). However, Φy leached cobalt (1.6 mg L−1), limiting its use for water treatment. To avoid leaching, Φy was calcinated, forming a mixed metal oxide (MMO). In the combination of MMO/PMS, no metals leached, the CIP adsorption was low (<20%), and the action of SO4•− dominated, leading to a synergistic effect on pollutant elimination (>95% after 15 min of treatment). MMO/PMS promoted the opening and oxidation of the piperazyl ring, plus the hydroxylation of the quinolone moiety on CIP, which potentially decreased the biological activity. After three reuse cycles, the MMO still presented with a high activation of PMS toward CIP degradation (90% in 15 min of action). Additionally, the CIP degradation by the MMO/PMS system in simulated hospital wastewater was close to that obtained in distilled water. This work provides relevant information on the stability of Co-, Cu-, and Cr-based materials under interaction with PMS and the strategies to obtain a proper catalyst to degrade CIP.Universidad de Antioquia. Vicerrectoría de investigación. Comité para el Desarrollo de la Investigación - CODIColombia. Ministerio de Ciencia, Tecnología e Innovación - MinCienciasCOL0001923COL0125116COL000861917 Páginasapplication/pdfengMDPIBasilea, Suizahttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessAttribution 4.0 Internationalhttp://purl.org/coar/access_right/c_abf2Scanning electron microscopesOxidaciónOxidationAntibacterianos - farmacologíaAnti-Bacterial Agents - pharmacologyCiprofloxacina - farmacologíaCiprofloxacin - pharmacologyCobaltCobreCopperPeróxidosPeroxidesContaminantes Químicos del Agua - análisisWater Pollutants, Chemical - analysisWater treatmentTratamiento del aguaScanning electron microscopyMicroscopía electrónica de barridoMetalsMetalChromate of copper and cobalthttp://aims.fao.org/aos/agrovoc/c_ef195799http://aims.fao.org/aos/agrovoc/c_a87b3af2http://aims.fao.org/aos/agrovoc/c_29036http://id.loc.gov/authorities/subjects/sh85117990https://id.nlm.nih.gov/mesh/D000900https://id.nlm.nih.gov/mesh/D002939https://id.nlm.nih.gov/mesh/D003035https://id.nlm.nih.gov/mesh/D003300https://id.nlm.nih.gov/mesh/D010545https://id.nlm.nih.gov/mesh/D014874ODS 6: Agua limpia y saneamiento. 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ltbywgc2kgZnVlcmUgYXBsaWNhYmxlKSwgeS9vIChpaSkgZWwgbm9tYnJlIGRlIGxhIHBhcnRlIG8gbGFzIHBhcnRlcyBxdWUgZWwgQXV0b3IgT3JpZ2luYWwgeS9vIGVsIExpY2VuY2lhbnRlIGh1YmllcmVuIGRlc2lnbmFkbyBwYXJhIGxhIGF0cmlidWNpw7NuICh2LmcuLCB1biBpbnN0aXR1dG8gcGF0cm9jaW5hZG9yLCBlZGl0b3JpYWwsIHB1YmxpY2FjacOzbikgZW4gbGEgaW5mb3JtYWNpw7NuIGRlIGxvcyBkZXJlY2hvcyBkZSBhdXRvciBkZWwgTGljZW5jaWFudGUsIHTDqXJtaW5vcyBkZSBzZXJ2aWNpb3MgbyBkZSBvdHJhcyBmb3JtYXMgcmF6b25hYmxlczsgZWwgdMOtdHVsbyBkZSBsYSBPYnJhIHNpIGVzdMOhIHByb3Zpc3RvOyBlbiBsYSBtZWRpZGEgZGUgbG8gcmF6b25hYmxlbWVudGUgZmFjdGlibGUgeSwgc2kgZXN0w6EgcHJvdmlzdG8sIGVsIElkZW50aWZpY2Fkb3IgVW5pZm9ybWUgZGUgUmVjdXJzb3MgKFVuaWZvcm0gUmVzb3VyY2UgSWRlbnRpZmllcikgcXVlIGVsIExpY2VuY2lhbnRlIGVzcGVjaWZpY2EgcGFyYSBzZXIgYXNvY2lhZG8gY29uIGxhIE9icmEsIHNhbHZvIHF1ZSB0YWwgVVJJIG5vIHNlIHJlZmllcmEgYSBsYSBub3RhIHNvYnJlIGxvcyBkZXJlY2hvcyBkZSBhdXRvciBvIGEgbGEgaW5mb3JtYWNpw7NuIHNvYnJlIGVsIGxpY2VuY2lhbWllbnRvIGRlIGxhIE9icmE7IHkgZW4gZWwgY2FzbyBkZSB1bmEgT2JyYSBEZXJpdmFkYSwgYXRyaWJ1aXIgZWwgY3LDqWRpdG8gaWRlbnRpZmljYW5kbyBlbCB1c28gZGUgbGEgT2JyYSBlbiBsYSBPYnJhIERlcml2YWRhICh2LmcuLCAiVHJhZHVjY2nDs24gRnJhbmNlc2EgZGUgbGEgT2JyYSBkZWwgQXV0b3IgT3JpZ2luYWwsIiBvICJHdWnDs24gQ2luZW1hdG9ncsOhZmljbyBiYXNhZG8gZW4gbGEgT2JyYSBvcmlnaW5hbCBkZWwgQXV0b3IgT3JpZ2luYWwiKS4gVGFsIGNyw6lkaXRvIHB1ZWRlIHNlciBpbXBsZW1lbnRhZG8gZGUgY3VhbHF1aWVyIGZvcm1hIHJhem9uYWJsZTsgZW4gZWwgY2Fzbywgc2luIGVtYmFyZ28sIGRlIE9icmFzIERlcml2YWRhcyB1IE9icmFzIENvbGVjdGl2YXMsIHRhbCBjcsOpZGl0byBhcGFyZWNlcsOhLCBjb21vIG3DrW5pbW8sIGRvbmRlIGFwYXJlY2UgZWwgY3LDqWRpdG8gZGUgY3VhbHF1aWVyIG90cm8gYXV0b3IgY29tcGFyYWJsZSB5IGRlIHVuYSBtYW5lcmEsIGFsIG1lbm9zLCB0YW4gZGVzdGFjYWRhIGNvbW8gZWwgY3LDqWRpdG8gZGUgb3RybyBhdXRvciBjb21wYXJhYmxlLiAgCmQuIFBhcmEgZXZpdGFyIHRvZGEgY29uZnVzacOzbiwgZWwgTGljZW5jaWFudGUgYWNsYXJhIHF1ZSwgY3VhbmRvIGxhIG9icmEgZXMgdW5hIGNvbXBvc2ljacOzbiBtdXNpY2FsOgoKaS4gUmVnYWzDrWFzIHBvciBpbnRlcnByZXRhY2nDs24geSBlamVjdWNpw7NuIGJham8gbGljZW5jaWFzIGdlbmVyYWxlcy4gRWwgTGljZW5jaWFudGUgc2UgcmVzZXJ2YSBlbCBkZXJlY2hvIGV4Y2x1c2l2byBkZSBhdXRvcml6YXIgbGEgZWplY3VjacOzbiBww7pibGljYSBvIGxhIGVqZWN1Y2nDs24gcMO6YmxpY2EgZGlnaXRhbCBkZSBsYSBvYnJhIHkgZGUgcmVjb2xlY3Rhciwgc2VhIGluZGl2aWR1YWxtZW50ZSBvIGEgdHJhdsOpcyBkZSB1bmEgc29jaWVkYWQgZGUgZ2VzdGnDs24gY29sZWN0aXZhIGRlIGRlcmVjaG9zIGRlIGF1dG9yIHkgZGVyZWNob3MgY29uZXhvcyAocG9yIGVqZW1wbG8sIFNBWUNPKSwgbGFzIHJlZ2Fsw61hcyBwb3IgbGEgZWplY3VjacOzbiBww7pibGljYSBvIHBvciBsYSBlamVjdWNpw7NuIHDDumJsaWNhIGRpZ2l0YWwgZGUgbGEgb2JyYSAocG9yIGVqZW1wbG8gV2ViY2FzdCkgbGljZW5jaWFkYSBiYWpvIGxpY2VuY2lhcyBnZW5lcmFsZXMsIHNpIGxhIGludGVycHJldGFjacOzbiBvIGVqZWN1Y2nDs24gZGUgbGEgb2JyYSBlc3TDoSBwcmltb3JkaWFsbWVudGUgb3JpZW50YWRhIHBvciBvIGRpcmlnaWRhIGEgbGEgb2J0ZW5jacOzbiBkZSB1bmEgdmVudGFqYSBjb21lcmNpYWwgbyB1bmEgY29tcGVuc2FjacOzbiBtb25ldGFyaWEgcHJpdmFkYS4KaWkuIFJlZ2Fsw61hcyBwb3IgRm9ub2dyYW1hcy4gRWwgTGljZW5jaWFudGUgc2UgcmVzZXJ2YSBlbCBkZXJlY2hvIGV4Y2x1c2l2byBkZSByZWNvbGVjdGFyLCBpbmRpdmlkdWFsbWVudGUgbyBhIHRyYXbDqXMgZGUgdW5hIHNvY2llZGFkIGRlIGdlc3Rpw7NuIGNvbGVjdGl2YSBkZSBkZXJlY2hvcyBkZSBhdXRvciB5IGRlcmVjaG9zIGNvbmV4b3MgKHBvciBlamVtcGxvLCBsb3MgY29uc2FncmFkb3MgcG9yIGxhIFNBWUNPKSwgdW5hIGFnZW5jaWEgZGUgZGVyZWNob3MgbXVzaWNhbGVzIG8gYWxnw7puIGFnZW50ZSBkZXNpZ25hZG8sIGxhcyByZWdhbMOtYXMgcG9yIGN1YWxxdWllciBmb25vZ3JhbWEgcXVlIFVzdGVkIGNyZWUgYSBwYXJ0aXIgZGUgbGEgb2JyYSAo4oCcdmVyc2nDs24gY292ZXLigJ0pIHkgZGlzdHJpYnV5YSwgZW4gbG9zIHTDqXJtaW5vcyBkZWwgcsOpZ2ltZW4gZGUgZGVyZWNob3MgZGUgYXV0b3IsIHNpIGxhIGNyZWFjacOzbiBvIGRpc3RyaWJ1Y2nDs24gZGUgZXNhIHZlcnNpw7NuIGNvdmVyIGVzdMOhIHByaW1vcmRpYWxtZW50ZSBkZXN0aW5hZGEgbyBkaXJpZ2lkYSBhIG9idGVuZXIgdW5hIHZlbnRhamEgY29tZXJjaWFsIG8gdW5hIGNvbXBlbnNhY2nDs24gbW9uZXRhcmlhIHByaXZhZGEuCiAgICAgIAplLiBHZXN0acOzbiBkZSBEZXJlY2hvcyBkZSBBdXRvciBzb2JyZSBJbnRlcnByZXRhY2lvbmVzIHkgRWplY3VjaW9uZXMgRGlnaXRhbGVzIChXZWJDYXN0aW5nKS4gUGFyYSBldml0YXIgdG9kYSBjb25mdXNpw7NuLCBlbCBMaWNlbmNpYW50ZSBhY2xhcmEgcXVlLCBjdWFuZG8gbGEgb2JyYSBzZWEgdW4gZm9ub2dyYW1hLCBlbCBMaWNlbmNpYW50ZSBzZSByZXNlcnZhIGVsIGRlcmVjaG8gZXhjbHVzaXZvIGRlIGF1dG9yaXphciBsYSBlamVjdWNpw7NuIHDDumJsaWNhIGRpZ2l0YWwgZGUgbGEgb2JyYSAocG9yIGVqZW1wbG8sIHdlYmNhc3QpIHkgZGUgcmVjb2xlY3RhciwgaW5kaXZpZHVhbG1lbnRlIG8gYSB0cmF2w6lzIGRlIHVuYSBzb2NpZWRhZCBkZSBnZXN0acOzbiBjb2xlY3RpdmEgZGUgZGVyZWNob3MgZGUgYXV0b3IgeSBkZXJlY2hvcyBjb25leG9zIChwb3IgZWplbXBsbywgQUNJTlBSTyksIGxhcyByZWdhbMOtYXMgcG9yIGxhIGVqZWN1Y2nDs24gcMO6YmxpY2EgZGlnaXRhbCBkZSBsYSBvYnJhIChwb3IgZWplbXBsbywgd2ViY2FzdCksIHN1amV0YSBhIGxhcyBkaXNwb3NpY2lvbmVzIGFwbGljYWJsZXMgZGVsIHLDqWdpbWVuIGRlIERlcmVjaG8gZGUgQXV0b3IsIHNpIGVzdGEgZWplY3VjacOzbiBww7pibGljYSBkaWdpdGFsIGVzdMOhIHByaW1vcmRpYWxtZW50ZSBkaXJpZ2lkYSBhIG9idGVuZXIgdW5hIHZlbnRhamEgY29tZXJjaWFsIG8gdW5hIGNvbXBlbnNhY2nDs24gbW9uZXRhcmlhIHByaXZhZGEuCiAgCjUuIFJlcHJlc2VudGFjaW9uZXMsIEdhcmFudMOtYXMgeSBMaW1pdGFjaW9uZXMgZGUgUmVzcG9uc2FiaWxpZGFkLgpBIE1FTk9TIFFVRSBMQVMgUEFSVEVTIExPIEFDT1JEQVJBTiBERSBPVFJBIEZPUk1BIFBPUiBFU0NSSVRPLCBFTCBMSUNFTkNJQU5URSBPRlJFQ0UgTEEgT0JSQSAoRU4gRUwgRVNUQURPIEVOIEVMIFFVRSBTRSBFTkNVRU5UUkEpIOKAnFRBTCBDVUFM4oCdLCBTSU4gQlJJTkRBUiBHQVJBTlTDjUFTIERFIENMQVNFIEFMR1VOQSBSRVNQRUNUTyBERSBMQSBPQlJBLCBZQSBTRUEgRVhQUkVTQSwgSU1QTMONQ0lUQSwgTEVHQUwgTyBDVUFMUVVJRVJBIE9UUkEsIElOQ0xVWUVORE8sIFNJTiBMSU1JVEFSU0UgQSBFTExBUywgR0FSQU5Uw41BUyBERSBUSVRVTEFSSURBRCwgQ09NRVJDSUFCSUxJREFELCBBREFQVEFCSUxJREFEIE8gQURFQ1VBQ0nDk04gQSBQUk9Qw5NTSVRPIERFVEVSTUlOQURPLCBBVVNFTkNJQSBERSBJTkZSQUNDScOTTiwgREUgQVVTRU5DSUEgREUgREVGRUNUT1MgTEFURU5URVMgTyBERSBPVFJPIFRJUE8sIE8gTEEgUFJFU0VOQ0lBIE8gQVVTRU5DSUEgREUgRVJST1JFUywgU0VBTiBPIE5PIERFU0NVQlJJQkxFUyAoUFVFREFOIE8gTk8gU0VSIEVTVE9TIERFU0NVQklFUlRPUykuIEFMR1VOQVMgSlVSSVNESUNDSU9ORVMgTk8gUEVSTUlURU4gTEEgRVhDTFVTScOTTiBERSBHQVJBTlTDjUFTIElNUEzDjUNJVEFTLCBFTiBDVVlPIENBU08gRVNUQSBFWENMVVNJw5NOIFBVRURFIE5PIEFQTElDQVJTRSBBIFVTVEVELgogIAo2LiBMaW1pdGFjacOzbiBkZSByZXNwb25zYWJpbGlkYWQuCkEgTUVOT1MgUVVFIExPIEVYSUpBIEVYUFJFU0FNRU5URSBMQSBMRVkgQVBMSUNBQkxFLCBFTCBMSUNFTkNJQU5URSBOTyBTRVLDgSBSRVNQT05TQUJMRSBBTlRFIFVTVEVEIFBPUiBEQcORTyBBTEdVTk8sIFNFQSBQT1IgUkVTUE9OU0FCSUxJREFEIEVYVFJBQ09OVFJBQ1RVQUwsIFBSRUNPTlRSQUNUVUFMIE8gQ09OVFJBQ1RVQUwsIE9CSkVUSVZBIE8gU1VCSkVUSVZBLCBTRSBUUkFURSBERSBEQcORT1MgTU9SQUxFUyBPIFBBVFJJTU9OSUFMRVMsIERJUkVDVE9TIE8gSU5ESVJFQ1RPUywgUFJFVklTVE9TIE8gSU1QUkVWSVNUT1MgUFJPRFVDSURPUyBQT1IgRUwgVVNPIERFIEVTVEEgTElDRU5DSUEgTyBERSBMQSBPQlJBLCBBVU4gQ1VBTkRPIEVMIExJQ0VOQ0lBTlRFIEhBWUEgU0lETyBBRFZFUlRJRE8gREUgTEEgUE9TSUJJTElEQUQgREUgRElDSE9TIERBw5FPUy4gQUxHVU5BUyBMRVlFUyBOTyBQRVJNSVRFTiBMQSBFWENMVVNJw5NOIERFIENJRVJUQSBSRVNQT05TQUJJTElEQUQsIEVOIENVWU8gQ0FTTyBFU1RBIEVYQ0xVU0nDk04gUFVFREUgTk8gQVBMSUNBUlNFIEEgVVNURUQuCiAgCjcuIFTDqXJtaW5vLgkKYS4gRXN0YSBMaWNlbmNpYSB5IGxvcyBkZXJlY2hvcyBvdG9yZ2Fkb3MgZW4gdmlydHVkIGRlIGVsbGEgdGVybWluYXLDoW4gYXV0b23DoXRpY2FtZW50ZSBzaSBVc3RlZCBpbmZyaW5nZSBhbGd1bmEgY29uZGljacOzbiBlc3RhYmxlY2lkYSBlbiBlbGxhLiBTaW4gZW1iYXJnbywgbG9zIGluZGl2aWR1b3MgbyBlbnRpZGFkZXMgcXVlIGhhbiByZWNpYmlkbyBPYnJhcyBEZXJpdmFkYXMgbyBDb2xlY3RpdmFzIGRlIFVzdGVkIGRlIGNvbmZvcm1pZGFkIGNvbiBlc3RhIExpY2VuY2lhLCBubyB2ZXLDoW4gdGVybWluYWRhcyBzdXMgbGljZW5jaWFzLCBzaWVtcHJlIHF1ZSBlc3RvcyBpbmRpdmlkdW9zIG8gZW50aWRhZGVzIHNpZ2FuIGN1bXBsaWVuZG8gw61udGVncmFtZW50ZSBsYXMgY29uZGljaW9uZXMgZGUgZXN0YXMgbGljZW5jaWFzLiBMYXMgU2VjY2lvbmVzIDEsIDIsIDUsIDYsIDcsIHkgOCBzdWJzaXN0aXLDoW4gYSBjdWFscXVpZXIgdGVybWluYWNpw7NuIGRlIGVzdGEgTGljZW5jaWEuCmIuIFN1amV0YSBhIGxhcyBjb25kaWNpb25lcyB5IHTDqXJtaW5vcyBhbnRlcmlvcmVzLCBsYSBsaWNlbmNpYSBvdG9yZ2FkYSBhcXXDrSBlcyBwZXJwZXR1YSAoZHVyYW50ZSBlbCBwZXLDrW9kbyBkZSB2aWdlbmNpYSBkZSBsb3MgZGVyZWNob3MgZGUgYXV0b3IgZGUgbGEgb2JyYSkuIE5vIG9ic3RhbnRlIGxvIGFudGVyaW9yLCBlbCBMaWNlbmNpYW50ZSBzZSByZXNlcnZhIGVsIGRlcmVjaG8gYSBwdWJsaWNhciB5L28gZXN0cmVuYXIgbGEgT2JyYSBiYWpvIGNvbmRpY2lvbmVzIGRlIGxpY2VuY2lhIGRpZmVyZW50ZXMgbyBhIGRlamFyIGRlIGRpc3RyaWJ1aXJsYSBlbiBsb3MgdMOpcm1pbm9zIGRlIGVzdGEgTGljZW5jaWEgZW4gY3VhbHF1aWVyIG1vbWVudG87IGVuIGVsIGVudGVuZGlkbywgc2luIGVtYmFyZ28sIHF1ZSBlc2EgZWxlY2Npw7NuIG5vIHNlcnZpcsOhIHBhcmEgcmV2b2NhciBlc3RhIGxpY2VuY2lhIG8gcXVlIGRlYmEgc2VyIG90b3JnYWRhICwgYmFqbyBsb3MgdMOpcm1pbm9zIGRlIGVzdGEgbGljZW5jaWEpLCB5IGVzdGEgbGljZW5jaWEgY29udGludWFyw6EgZW4gcGxlbm8gdmlnb3IgeSBlZmVjdG8gYSBtZW5vcyBxdWUgc2VhIHRlcm1pbmFkYSBjb21vIHNlIGV4cHJlc2EgYXRyw6FzLiBMYSBMaWNlbmNpYSByZXZvY2FkYSBjb250aW51YXLDoSBzaWVuZG8gcGxlbmFtZW50ZSB2aWdlbnRlIHkgZWZlY3RpdmEgc2kgbm8gc2UgbGUgZGEgdMOpcm1pbm8gZW4gbGFzIGNvbmRpY2lvbmVzIGluZGljYWRhcyBhbnRlcmlvcm1lbnRlLgogIAo4LiBWYXJpb3MuCmEuIENhZGEgdmV6IHF1ZSBVc3RlZCBkaXN0cmlidXlhIG8gcG9uZ2EgYSBkaXNwb3NpY2nDs24gcMO6YmxpY2EgbGEgT2JyYSBvIHVuYSBPYnJhIENvbGVjdGl2YSwgZWwgTGljZW5jaWFudGUgb2ZyZWNlcsOhIGFsIGRlc3RpbmF0YXJpbyB1bmEgbGljZW5jaWEgZW4gbG9zIG1pc21vcyB0w6lybWlub3MgeSBjb25kaWNpb25lcyBxdWUgbGEgbGljZW5jaWEgb3RvcmdhZGEgYSBVc3RlZCBiYWpvIGVzdGEgTGljZW5jaWEuCmIuIFNpIGFsZ3VuYSBkaXNwb3NpY2nDs24gZGUgZXN0YSBMaWNlbmNpYSByZXN1bHRhIGludmFsaWRhZGEgbyBubyBleGlnaWJsZSwgc2Vnw7puIGxhIGxlZ2lzbGFjacOzbiB2aWdlbnRlLCBlc3RvIG5vIGFmZWN0YXLDoSBuaSBsYSB2YWxpZGV6IG5pIGxhIGFwbGljYWJpbGlkYWQgZGVsIHJlc3RvIGRlIGNvbmRpY2lvbmVzIGRlIGVzdGEgTGljZW5jaWEgeSwgc2luIGFjY2nDs24gYWRpY2lvbmFsIHBvciBwYXJ0ZSBkZSBsb3Mgc3VqZXRvcyBkZSBlc3RlIGFjdWVyZG8sIGFxdcOpbGxhIHNlIGVudGVuZGVyw6EgcmVmb3JtYWRhIGxvIG3DrW5pbW8gbmVjZXNhcmlvIHBhcmEgaGFjZXIgcXVlIGRpY2hhIGRpc3Bvc2ljacOzbiBzZWEgdsOhbGlkYSB5IGV4aWdpYmxlLgpjLiBOaW5nw7puIHTDqXJtaW5vIG8gZGlzcG9zaWNpw7NuIGRlIGVzdGEgTGljZW5jaWEgc2UgZXN0aW1hcsOhIHJlbnVuY2lhZGEgeSBuaW5ndW5hIHZpb2xhY2nDs24gZGUgZWxsYSBzZXLDoSBjb25zZW50aWRhIGEgbWVub3MgcXVlIGVzYSByZW51bmNpYSBvIGNvbnNlbnRpbWllbnRvIHNlYSBvdG9yZ2FkbyBwb3IgZXNjcml0byB5IGZpcm1hZG8gcG9yIGxhIHBhcnRlIHF1ZSByZW51bmNpZSBvIGNvbnNpZW50YS4KZC4gRXN0YSBMaWNlbmNpYSByZWZsZWphIGVsIGFjdWVyZG8gcGxlbm8gZW50cmUgbGFzIHBhcnRlcyByZXNwZWN0byBhIGxhIE9icmEgYXF1w60gbGljZW5jaWFkYS4gTm8gaGF5IGFycmVnbG9zLCBhY3VlcmRvcyBvIGRlY2xhcmFjaW9uZXMgcmVzcGVjdG8gYSBsYSBPYnJhIHF1ZSBubyBlc3TDqW4gZXNwZWNpZmljYWRvcyBlbiBlc3RlIGRvY3VtZW50by4gRWwgTGljZW5jaWFudGUgbm8gc2UgdmVyw6EgbGltaXRhZG8gcG9yIG5pbmd1bmEgZGlzcG9zaWNpw7NuIGFkaWNpb25hbCBxdWUgcHVlZGEgc3VyZ2lyIGVuIGFsZ3VuYSBjb211bmljYWNpw7NuIGVtYW5hZGEgZGUgVXN0ZWQuIEVzdGEgTGljZW5jaWEgbm8gcHVlZGUgc2VyIG1vZGlmaWNhZGEgc2luIGVsIGNvbnNlbnRpbWllbnRvIG11dHVvIHBvciBlc2NyaXRvIGRlbCBMaWNlbmNpYW50ZSB5IFVzdGVkLgo=