Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD)
Per- and polyfluoroalkyl substances are widely used in various consumer products. However, these compounds can cause various harm to the environment and health. Considering the high chemical stability, these compounds are not completely removed from the aqueous environment, and consequently, recent...
- Autores:
-
da Silva Bruckmann, Franciele
Jemli, Sonia
Ben Amara, Fakhreddine
Adelodun, Bashir
Silva Oliveira, Luis Felipe
Bejar, Samir
Rizwan Khan, Mohammad
Ahmad, Naushad
Simões dos Reis, Glaydson
Dotto, Guilherme Luiz
- Tipo de recurso:
- Article of investigation
- Fecha de publicación:
- 2024
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/13304
- Acceso en línea:
- https://hdl.handle.net/11323/13304
https://repositorio.cuc.edu.co/
- Palabra clave:
- Adsorption
Emerging contaminants
β-cyclodextrin
Recalcitrant compounds
- Rights
- embargoedAccess
- License
- Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)
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| dc.title.eng.fl_str_mv |
Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD) |
| title |
Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD) |
| spellingShingle |
Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD) Adsorption Emerging contaminants β-cyclodextrin Recalcitrant compounds |
| title_short |
Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD) |
| title_full |
Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD) |
| title_fullStr |
Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD) |
| title_full_unstemmed |
Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD) |
| title_sort |
Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD) |
| dc.creator.fl_str_mv |
da Silva Bruckmann, Franciele Jemli, Sonia Ben Amara, Fakhreddine Adelodun, Bashir Silva Oliveira, Luis Felipe Bejar, Samir Rizwan Khan, Mohammad Ahmad, Naushad Simões dos Reis, Glaydson Dotto, Guilherme Luiz |
| dc.contributor.author.none.fl_str_mv |
da Silva Bruckmann, Franciele Jemli, Sonia Ben Amara, Fakhreddine Adelodun, Bashir Silva Oliveira, Luis Felipe Bejar, Samir Rizwan Khan, Mohammad Ahmad, Naushad Simões dos Reis, Glaydson Dotto, Guilherme Luiz |
| dc.subject.proposal.eng.fl_str_mv |
Adsorption Emerging contaminants β-cyclodextrin Recalcitrant compounds |
| topic |
Adsorption Emerging contaminants β-cyclodextrin Recalcitrant compounds |
| description |
Per- and polyfluoroalkyl substances are widely used in various consumer products. However, these compounds can cause various harm to the environment and health. Considering the high chemical stability, these compounds are not completely removed from the aqueous environment, and consequently, recent studies have detected their presence in water bodies. In this scenario, biomass-based adsorbents are promising. β-cyclodextrin (β-CD) was grafted in an ultrafine potato peel waste (UFPPW) to produce a novel, efficient, and sustainable adsorbent (UFPPW-β-CD) that was used to remove three different perfluorosulfonic acids (PFSAs) from water. The efficient grafting was proved by several characterization techniques, which also demonstrated the main UFPPW-β-CD features. The UFPPW-β-CD was efficient for all PFSAs (perfluorohexanesulfonic acid (PFHxS), perfluoropentanesulfonic acid (PFPeS), and perfluorobutanesulfonic acid (PFBS)), with removal percentage higher than 74 %. The increase in the Csingle bondF chain of PFSAs favored the adsorption due to the host–guest hydrophobic interactions between the Csingle bondF chains of the adsorbates and the hydrophobic cavity of the β-CD. Removal percentages and adsorption capacities at pH 3.0 were 74.6 % (49.92 µg g−1) to the PFBS, 82.6 % (65.66 µg g−1) to the PFPeS, and 90 % (100.89 µg g−1) to the PFHxS. The kinetic followed the General order model, while the equilibrium agreed with the Sips isotherm. The adsorption capacity increased with the increase in the Csingle bondF chain of the adsorbate, but the adsorption rate followed the opposite trend. PFSAs adsorption on the UFPPW-β-CD adsorbent was favorable and exothermic. UFPPW-β-CD could be used seven times, keeping its maximum adsorption capacity constant using ultrasound-assisted desorption. It can be concluded that UFPPW-β-CD is a sustainable adsorbent to uptake PFSAs from water, and this process is dependent on the size of the Csingle bondF chains. |
| publishDate |
2024 |
| dc.date.accessioned.none.fl_str_mv |
2024-09-09T15:35:01Z |
| dc.date.available.none.fl_str_mv |
2024-09-09T15:35:01Z 2026-12-18 |
| dc.date.issued.none.fl_str_mv |
2024-12-18 |
| dc.type.spa.fl_str_mv |
Artículo de revista |
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http://purl.org/coar/resource_type/c_2df8fbb1 |
| dc.type.content.spa.fl_str_mv |
Text |
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info:eu-repo/semantics/article |
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http://purl.org/redcol/resource_type/ART |
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info:eu-repo/semantics/publishedVersion |
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http://purl.org/coar/version/c_970fb48d4fbd8a85 |
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http://purl.org/coar/resource_type/c_2df8fbb1 |
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publishedVersion |
| dc.identifier.citation.spa.fl_str_mv |
Franciele da Silva Bruckmann, Sonia Jemli, Fakhreddine Ben Amara, Bashir Adelodun, Luis Felipe Oliveira Silva, Samir Bejar, Mohammad Rizwan Khan, Naushad Ahmad, Glaydson Simões dos Reis, Guilherme Luiz Dotto, Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD), Separation and Purification Technology, Volume 350, 2024, 127972, ISSN 1383-5866, https://doi.org/10.1016/j.seppur.2024.127972. |
| dc.identifier.issn.spa.fl_str_mv |
1383-5866 |
| dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/11323/13304 |
| dc.identifier.doi.none.fl_str_mv |
10.1016/j.seppur.2024.127972 |
| dc.identifier.eissn.spa.fl_str_mv |
1873-3794 |
| dc.identifier.instname.spa.fl_str_mv |
Corporación Universidad de la Costa |
| dc.identifier.reponame.spa.fl_str_mv |
REDICUC - Repositorio CUC |
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https://repositorio.cuc.edu.co/ |
| identifier_str_mv |
Franciele da Silva Bruckmann, Sonia Jemli, Fakhreddine Ben Amara, Bashir Adelodun, Luis Felipe Oliveira Silva, Samir Bejar, Mohammad Rizwan Khan, Naushad Ahmad, Glaydson Simões dos Reis, Guilherme Luiz Dotto, Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD), Separation and Purification Technology, Volume 350, 2024, 127972, ISSN 1383-5866, https://doi.org/10.1016/j.seppur.2024.127972. 1383-5866 10.1016/j.seppur.2024.127972 1873-3794 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
| url |
https://hdl.handle.net/11323/13304 https://repositorio.cuc.edu.co/ |
| dc.language.iso.spa.fl_str_mv |
eng |
| language |
eng |
| dc.relation.ispartofjournal.spa.fl_str_mv |
Separation and Purification Technology |
| dc.relation.references.spa.fl_str_mv |
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Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.https://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/embargoedAccesshttp://purl.org/coar/access_right/c_f1cfda Silva Bruckmann, FrancieleJemli, SoniaBen Amara, FakhreddineAdelodun, BashirSilva Oliveira, Luis FelipeBejar, SamirRizwan Khan, MohammadAhmad, NaushadSimões dos Reis, GlaydsonDotto, Guilherme Luiz2024-09-09T15:35:01Z2026-12-182024-09-09T15:35:01Z2024-12-18Franciele da Silva Bruckmann, Sonia Jemli, Fakhreddine Ben Amara, Bashir Adelodun, Luis Felipe Oliveira Silva, Samir Bejar, Mohammad Rizwan Khan, Naushad Ahmad, Glaydson Simões dos Reis, Guilherme Luiz Dotto, Adsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD), Separation and Purification Technology, Volume 350, 2024, 127972, ISSN 1383-5866, https://doi.org/10.1016/j.seppur.2024.127972.1383-5866https://hdl.handle.net/11323/1330410.1016/j.seppur.2024.1279721873-3794Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/Per- and polyfluoroalkyl substances are widely used in various consumer products. However, these compounds can cause various harm to the environment and health. Considering the high chemical stability, these compounds are not completely removed from the aqueous environment, and consequently, recent studies have detected their presence in water bodies. In this scenario, biomass-based adsorbents are promising. β-cyclodextrin (β-CD) was grafted in an ultrafine potato peel waste (UFPPW) to produce a novel, efficient, and sustainable adsorbent (UFPPW-β-CD) that was used to remove three different perfluorosulfonic acids (PFSAs) from water. The efficient grafting was proved by several characterization techniques, which also demonstrated the main UFPPW-β-CD features. The UFPPW-β-CD was efficient for all PFSAs (perfluorohexanesulfonic acid (PFHxS), perfluoropentanesulfonic acid (PFPeS), and perfluorobutanesulfonic acid (PFBS)), with removal percentage higher than 74 %. The increase in the Csingle bondF chain of PFSAs favored the adsorption due to the host–guest hydrophobic interactions between the Csingle bondF chains of the adsorbates and the hydrophobic cavity of the β-CD. Removal percentages and adsorption capacities at pH 3.0 were 74.6 % (49.92 µg g−1) to the PFBS, 82.6 % (65.66 µg g−1) to the PFPeS, and 90 % (100.89 µg g−1) to the PFHxS. The kinetic followed the General order model, while the equilibrium agreed with the Sips isotherm. The adsorption capacity increased with the increase in the Csingle bondF chain of the adsorbate, but the adsorption rate followed the opposite trend. PFSAs adsorption on the UFPPW-β-CD adsorbent was favorable and exothermic. UFPPW-β-CD could be used seven times, keeping its maximum adsorption capacity constant using ultrasound-assisted desorption. It can be concluded that UFPPW-β-CD is a sustainable adsorbent to uptake PFSAs from water, and this process is dependent on the size of the Csingle bondF chains.9 páginasapplication/pdfengElsevier B.V.Netherlandshttps://www.sciencedirect.com/science/article/pii/S1383586624017118?pes=vorAdsorption of perfluorosulfonic acids (PFSAs) on an ultrafine potato peel waste grafted β-cyclodextrin (UFPPW-β-CD)Artículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85Separation and Purification Technology[1] J. Borrull, A. Colom, J. Fabregas, F. Borrull, E. Pocurull, Presence, behaviour and removal of selected organic micropollutants through drinking water treatment, Chemosphere 276 (2021) 130023, https://doi.org/10.1016/j. chemosphere.2021.130023.[2] H. Ren, R. Troger, ¨ L. Ahrens, K. Wiberg, D. 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Kwon, Reversible adsorption and desorption of PFAS on inexpensive graphite adsorbents via alternating electric field, RSC Adv. 11 (2021) 34652–34659, https://doi.org/10.1039/D1RA04821J.91350AdsorptionEmerging contaminantsβ-cyclodextrinRecalcitrant compoundsPublicationORIGINALAdsorption of perfluorosulfonic acids.pdfAdsorption of perfluorosulfonic acids.pdfArtículoapplication/pdf5194342https://repositorio.cuc.edu.co/bitstreams/e2e4f399-9aeb-4a19-bbd5-1d43d015c9a7/downloade7daf2c2669dd109e11de0dfa352af39MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-814828https://repositorio.cuc.edu.co/bitstreams/e7ed7c72-2104-4787-b06a-3663206bc265/download2f9959eaf5b71fae44bbf9ec84150c7aMD52TEXTAdsorption of perfluorosulfonic acids.pdf.txtAdsorption of perfluorosulfonic acids.pdf.txtExtracted texttext/plain49570https://repositorio.cuc.edu.co/bitstreams/c476effa-23a1-490f-9332-8c9f1bb19faa/download84d25660f61679fd8f8949625d5df9a1MD53THUMBNAILAdsorption of perfluorosulfonic acids.pdf.jpgAdsorption of perfluorosulfonic acids.pdf.jpgGenerated Thumbnailimage/jpeg14500https://repositorio.cuc.edu.co/bitstreams/ab36b681-c2bf-44a3-9cfb-68a8976e69e4/downloadafe5998428d5b66c5e00b7142cd19ad3MD5411323/13304oai:repositorio.cuc.edu.co:11323/133042024-09-17 12:46:54.257https://creativecommons.org/licenses/by-nc-nd/4.0/© 2024 Elsevier B.V. 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ada en las Obras Colectivas.

b.	Distribuir copias o fonogramas de las Obras, exhibirlas públicamente, ejecutarlas públicamente y/o ponerlas a disposición pública, incluyéndolas como incorporadas en Obras Colectivas, según corresponda.

c.	Distribuir copias de las Obras Derivadas que se generen, exhibirlas públicamente, ejecutarlas públicamente y/o ponerlas a disposición pública.
Los derechos mencionados anteriormente pueden ser ejercidos en todos los medios y formatos, actualmente conocidos o que se inventen en el futuro. Los derechos antes mencionados incluyen el derecho a realizar dichas modificaciones en la medida que sean técnicamente necesarias para ejercer los derechos en otro medio o formatos, pero de otra manera usted no está autorizado para realizar obras derivadas. Todos los derechos no otorgados expresamente por el Licenciante quedan por este medio reservados, incluyendo pero sin limitarse a aquellos que se mencionan en las secciones 4(d) y 4(e).

4. Restricciones.
La licencia otorgada en la anterior Sección 3 está expresamente sujeta y limitada por las siguientes restricciones:

a.	Usted puede distribuir, exhibir públicamente, ejecutar públicamente, o poner a disposición pública la Obra sólo bajo las condiciones de esta Licencia, y Usted debe incluir una copia de esta licencia o del Identificador Universal de Recursos de la misma con cada copia de la Obra que distribuya, exhiba públicamente, ejecute públicamente o ponga a disposición pública. No es posible ofrecer o imponer ninguna condición sobre la Obra que altere o limite las condiciones de esta Licencia o el ejercicio de los derechos de los destinatarios otorgados en este documento. No es posible sublicenciar la Obra. Usted debe mantener intactos todos los avisos que hagan referencia a esta Licencia y a la cláusula de limitación de garantías. Usted no puede distribuir, exhibir públicamente, ejecutar públicamente, o poner a disposición pública la Obra con alguna medida tecnológica que controle el acceso o la utilización de ella de una forma que sea inconsistente con las condiciones de esta Licencia. Lo anterior se aplica a la Obra incorporada a una Obra Colectiva, pero esto no exige que la Obra Colectiva aparte de la obra misma quede sujeta a las condiciones de esta Licencia. Si Usted crea una Obra Colectiva, previo aviso de cualquier Licenciante debe, en la medida de lo posible, eliminar de la Obra Colectiva cualquier referencia a dicho Licenciante o al Autor Original, según lo solicitado por el Licenciante y conforme lo exige la cláusula 4(c).

b.	Usted no puede ejercer ninguno de los derechos que le han sido otorgados en la Sección 3 precedente de modo que estén principalmente destinados o directamente dirigidos a conseguir un provecho comercial o una compensación monetaria privada. El intercambio de la Obra por otras obras protegidas por derechos de autor, ya sea a través de un sistema para compartir archivos digitales (digital file-sharing) o de cualquier otra manera no será considerado como estar destinado principalmente o dirigido directamente a conseguir un provecho comercial o una compensación monetaria privada, siempre que no se realice un pago mediante una compensación monetaria en relación con el intercambio de obras protegidas por el derecho de autor.

c.	Si usted distribuye, exhibe públicamente, ejecuta públicamente o ejecuta públicamente en forma digital la Obra o cualquier Obra Derivada u Obra Colectiva, Usted debe mantener intacta toda la información de derecho de autor de la Obra y proporcionar, de forma razonable según el medio o manera que Usted esté utilizando: (i) el nombre del Autor Original si está provisto (o seudónimo, si fuere aplicable), y/o (ii) el nombre de la parte o las partes que el Autor Original y/o el Licenciante hubieren designado para la atribución (v.g., un instituto patrocinador, editorial, publicación) en la información de los derechos de autor del Licenciante, términos de servicios o de otras formas razonables; el título de la Obra si está provisto; en la medida de lo razonablemente factible y, si está provisto, el Identificador Uniforme de Recursos (Uniform Resource Identifier) que el Licenciante especifica para ser asociado con la Obra, salvo que tal URI no se refiera a la nota sobre los derechos de autor o a la información sobre el licenciamiento de la Obra; y en el caso de una Obra Derivada, atribuir el crédito identificando el uso de la Obra en la Obra Derivada (v.g., "Traducción Francesa de la Obra del Autor Original," o "Guión Cinematográfico basado en la Obra original del Autor Original"). Tal crédito puede ser implementado de cualquier forma razonable; en el caso, sin embargo, de Obras Derivadas u Obras Colectivas, tal crédito aparecerá, como mínimo, donde aparece el crédito de cualquier otro autor comparable y de una manera, al menos, tan destacada como el crédito de otro autor comparable.

d.	Para evitar toda confusión, el Licenciante aclara que, cuando la obra es una composición musical:

i.	Regalías por interpretación y ejecución bajo licencias generales. El Licenciante se reserva el derecho exclusivo de autorizar la ejecución pública o la ejecución pública digital de la obra y de recolectar, sea individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, SAYCO), las regalías por la ejecución pública o por la ejecución pública digital de la obra (por ejemplo Webcast) licenciada bajo licencias generales, si la interpretación o ejecución de la obra está primordialmente orientada por o dirigida a la obtención de una ventaja comercial o una compensación monetaria privada.

ii.	Regalías por Fonogramas. El Licenciante se reserva el derecho exclusivo de recolectar, individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, los consagrados por la SAYCO), una agencia de derechos musicales o algún agente designado, las regalías por cualquier fonograma que Usted cree a partir de la obra (“versión cover”) y distribuya, en los términos del régimen de derechos de autor, si la creación o distribución de esa versión cover está primordialmente destinada o dirigida a obtener una ventaja comercial o una compensación monetaria privada.

e.	Gestión de Derechos de Autor sobre Interpretaciones y Ejecuciones Digitales (WebCasting). Para evitar toda confusión, el Licenciante aclara que, cuando la obra sea un fonograma, el Licenciante se reserva el derecho exclusivo de autorizar la ejecución pública digital de la obra (por ejemplo, webcast) y de recolectar, individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, ACINPRO), las regalías por la ejecución pública digital de la obra (por ejemplo, webcast), sujeta a las disposiciones aplicables del régimen de Derecho de Autor, si esta ejecución pública digital está primordialmente dirigida a obtener una ventaja comercial o una compensación monetaria privada.

5. Representaciones, Garantías y Limitaciones de Responsabilidad.
A MENOS QUE LAS PARTES LO ACORDARAN DE OTRA FORMA POR ESCRITO, EL LICENCIANTE OFRECE LA OBRA (EN EL ESTADO EN EL QUE SE ENCUENTRA) “TAL CUAL”, SIN BRINDAR GARANTÍAS DE CLASE ALGUNA RESPECTO DE LA OBRA, YA SEA EXPRESA, IMPLÍCITA, LEGAL O CUALQUIERA OTRA, INCLUYENDO, SIN LIMITARSE A ELLAS, GARANTÍAS DE TITULARIDAD, COMERCIABILIDAD, ADAPTABILIDAD O ADECUACIÓN A PROPÓSITO DETERMINADO, AUSENCIA DE INFRACCIÓN, DE AUSENCIA DE DEFECTOS LATENTES O DE OTRO TIPO, O LA PRESENCIA O AUSENCIA DE ERRORES, SEAN O NO DESCUBRIBLES (PUEDAN O NO SER ESTOS DESCUBIERTOS). ALGUNAS JURISDICCIONES NO PERMITEN LA EXCLUSIÓN DE GARANTÍAS IMPLÍCITAS, EN CUYO CASO ESTA EXCLUSIÓN PUEDE NO APLICARSE A USTED.

6. Limitación de responsabilidad.
A MENOS QUE LO EXIJA EXPRESAMENTE LA LEY APLICABLE, EL LICENCIANTE NO SERÁ RESPONSABLE ANTE USTED POR DAÑO ALGUNO, SEA POR RESPONSABILIDAD EXTRACONTRACTUAL, PRECONTRACTUAL O CONTRACTUAL, OBJETIVA O SUBJETIVA, SE TRATE DE DAÑOS MORALES O PATRIMONIALES, DIRECTOS O INDIRECTOS, PREVISTOS O IMPREVISTOS PRODUCIDOS POR EL USO DE ESTA LICENCIA O DE LA OBRA, AUN CUANDO EL LICENCIANTE HAYA SIDO ADVERTIDO DE LA POSIBILIDAD DE DICHOS DAÑOS. ALGUNAS LEYES NO PERMITEN LA EXCLUSIÓN DE CIERTA RESPONSABILIDAD, EN CUYO CASO ESTA EXCLUSIÓN PUEDE NO APLICARSE A USTED.

7. Término.

a.	Esta Licencia y los derechos otorgados en virtud de ella terminarán automáticamente si Usted infringe alguna condición establecida en ella. Sin embargo, los individuos o entidades que han recibido Obras Derivadas o Colectivas de Usted de conformidad con esta Licencia, no verán terminadas sus licencias, siempre que estos individuos o entidades sigan cumpliendo íntegramente las condiciones de estas licencias. Las Secciones 1, 2, 5, 6, 7, y 8 subsistirán a cualquier terminación de esta Licencia.

b.	Sujeta a las condiciones y términos anteriores, la licencia otorgada aquí es perpetua (durante el período de vigencia de los derechos de autor de la obra). No obstante lo anterior, el Licenciante se reserva el derecho a publicar y/o estrenar la Obra bajo condiciones de licencia diferentes o a dejar de distribuirla en los términos de esta Licencia en cualquier momento; en el entendido, sin embargo, que esa elección no servirá para revocar esta licencia o que deba ser otorgada , bajo los términos de esta licencia), y esta licencia continuará en pleno vigor y efecto a menos que sea terminada como se expresa atrás. La Licencia revocada continuará siendo plenamente vigente y efectiva si no se le da término en las condiciones indicadas anteriormente.

8. Varios.

a.	Cada vez que Usted distribuya o ponga a disposición pública la Obra o una Obra Colectiva, el Licenciante ofrecerá al destinatario una licencia en los mismos términos y condiciones que la licencia otorgada a Usted bajo esta Licencia.

b.	Si alguna disposición de esta Licencia resulta invalidada o no exigible, según la legislación vigente, esto no afectará ni la validez ni la aplicabilidad del resto de condiciones de esta Licencia y, sin acción adicional por parte de los sujetos de este acuerdo, aquélla se entenderá reformada lo mínimo necesario para hacer que dicha disposición sea válida y exigible.

c.	Ningún término o disposición de esta Licencia se estimará renunciada y ninguna violación de ella será consentida a menos que esa renuncia o consentimiento sea otorgado por escrito y firmado por la parte que renuncie o consienta.

d.	Esta Licencia refleja el acuerdo pleno entre las partes respecto a la Obra aquí licenciada. No hay arreglos, acuerdos o declaraciones respecto a la Obra que no estén especificados en este documento. El Licenciante no se verá limitado por ninguna disposición adicional que pueda surgir en alguna comunicación emanada de Usted. Esta Licencia no puede ser modificada sin el consentimiento mutuo por escrito del Licenciante y Usted.
 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