Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer

This work analyzes the adsorption of cadmium, a potentially toxic pollutant, on biopolymers synthesized from shrimp shells, as a promising new adsorbent. Spectroscopic analysis, such as FTIR, ATD/ATG, XRD, and SEM/EDX techniques, were used to characterize chitin before it was exposed to cadmium ions...

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Autores:
Moussout, Hamou
Dehmani, Younes
Dison S.P., Franco
georgin, jordana
Daou, Ikram
Lamhasni, Taibi
Ilyas, Chabri
Ahlafi, Hammou
Taky, Mohamed
Shaim, Abdelillah
Sadik, Abouarnadasse
Tipo de recurso:
Article of investigation
Fecha de publicación:
2023
Institución:
Corporación Universidad de la Costa
Repositorio:
REDICUC - Repositorio CUC
Idioma:
eng
OAI Identifier:
oai:repositorio.cuc.edu.co:11323/10579
Acceso en línea:
https://hdl.handle.net/11323/10579
https://repositorio.cuc.edu.co/
Palabra clave:
Cadmium
Uptake mechanism
Chitin biopolymer
Rights
embargoedAccess
License
Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)
id RCUC2_88bb065806623d84e0a41bdb2a83ae3a
oai_identifier_str oai:repositorio.cuc.edu.co:11323/10579
network_acronym_str RCUC2
network_name_str REDICUC - Repositorio CUC
repository_id_str
dc.title.eng.fl_str_mv Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer
title Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer
spellingShingle Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer
Cadmium
Uptake mechanism
Chitin biopolymer
title_short Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer
title_full Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer
title_fullStr Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer
title_full_unstemmed Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer
title_sort Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer
dc.creator.fl_str_mv Moussout, Hamou
Dehmani, Younes
Dison S.P., Franco
georgin, jordana
Daou, Ikram
Lamhasni, Taibi
Ilyas, Chabri
Ahlafi, Hammou
Taky, Mohamed
Shaim, Abdelillah
Sadik, Abouarnadasse
dc.contributor.author.none.fl_str_mv Moussout, Hamou
Dehmani, Younes
Dison S.P., Franco
georgin, jordana
Daou, Ikram
Lamhasni, Taibi
Ilyas, Chabri
Ahlafi, Hammou
Taky, Mohamed
Shaim, Abdelillah
Sadik, Abouarnadasse
dc.subject.proposal.eng.fl_str_mv Cadmium
Uptake mechanism
Chitin biopolymer
topic Cadmium
Uptake mechanism
Chitin biopolymer
description This work analyzes the adsorption of cadmium, a potentially toxic pollutant, on biopolymers synthesized from shrimp shells, as a promising new adsorbent. Spectroscopic analysis, such as FTIR, ATD/ATG, XRD, and SEM/EDX techniques, were used to characterize chitin before it was exposed to cadmium ions. Experimental data indicate that Cd(II) adsorption proceeds with pseudo-second-order model kinetics and is influenced by increasing temperature. In the equilibrium, the maximum adsorption capacity obtained was 58.82 mg g−1 at a temperature of 308 K. Experiments to obtain adsorption data were performed at T = 298–318 K. The saturated adsorption capacities of Cd(II) range from 57.40 to 59.90 mg g−1. The application of the physics-statistics model indicates that the Cd(II) atoms are adsorbed on the surface of the chitosan forming a monolayer. In addition to that, the results also show that the adsorption affinity increases with the system temperature, resulting in higher affinity and an increase of 30% in the adsorption capacity. The adsorption energy was found to be around 2.5 kJ mol−1, indicating that the adsorption is physical and endothermic. The entropy was found to quickly increases (reaching a maximum value of 6 × 10−22 kJ mol−1 K−1) at low concentrations followed by the equilibrium after the 40 mg L−1, indicating that the equilibrium is quickly reached. The Gibbs free energy indicates that the process is spontaneous (ranging from −1.364 to −1.451 kJ mol−1) and that the energy tends to remain constant after 15 mg L−1. Last, the results indicate that the Cd(II) is adsorbed due to dipole–dipole interactions and possible coordination bounds. The results of tests on the adsorption of cadmium by chitin showed that this biopolymer could replace other more expensive adsorbents.
publishDate 2023
dc.date.accessioned.none.fl_str_mv 2023-11-08T21:12:16Z
dc.date.available.none.fl_str_mv 2023-11-08T21:12:16Z
2025
dc.date.issued.none.fl_str_mv 2023
dc.type.spa.fl_str_mv Artículo de revista
dc.type.coar.spa.fl_str_mv http://purl.org/coar/resource_type/c_2df8fbb1
dc.type.content.spa.fl_str_mv Text
dc.type.driver.spa.fl_str_mv info:eu-repo/semantics/article
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dc.type.version.spa.fl_str_mv info:eu-repo/semantics/draft
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dc.identifier.citation.spa.fl_str_mv Hamou Moussout, Younes Dehmani, Dison S.P. Franco, Jordana Georgin, Ikram Daou, Taibi Lamhasni, Chabri Ilyas, Hammou Ahlafi, Mohamed Taky, Abdelillah Shaim, Abouarnadasse Sadik, Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer, Journal of Molecular Liquids, Volume 383, 2023, 122106, ISSN 0167-7322, https://doi.org/10.1016/j.molliq.2023.122106
dc.identifier.issn.spa.fl_str_mv 0167-7322
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/11323/10579
dc.identifier.doi.none.fl_str_mv 10.1016/j.molliq.2023.122106
dc.identifier.eissn.spa.fl_str_mv 1873-3166
dc.identifier.instname.spa.fl_str_mv Corporación Universidad de la Costa
dc.identifier.reponame.spa.fl_str_mv REDICUC - Repositorio CUC
dc.identifier.repourl.spa.fl_str_mv https://repositorio.cuc.edu.co/
identifier_str_mv Hamou Moussout, Younes Dehmani, Dison S.P. Franco, Jordana Georgin, Ikram Daou, Taibi Lamhasni, Chabri Ilyas, Hammou Ahlafi, Mohamed Taky, Abdelillah Shaim, Abouarnadasse Sadik, Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer, Journal of Molecular Liquids, Volume 383, 2023, 122106, ISSN 0167-7322, https://doi.org/10.1016/j.molliq.2023.122106
0167-7322
10.1016/j.molliq.2023.122106
1873-3166
Corporación Universidad de la Costa
REDICUC - Repositorio CUC
url https://hdl.handle.net/11323/10579
https://repositorio.cuc.edu.co/
dc.language.iso.spa.fl_str_mv eng
language eng
dc.relation.ispartofjournal.spa.fl_str_mv Journal of Molecular Liquids
dc.relation.citationvolume.spa.fl_str_mv 383
dc.rights.eng.fl_str_mv © 2023 Elsevier B.V. All rights reserved.
dc.rights.license.spa.fl_str_mv Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)
dc.rights.uri.spa.fl_str_mv https://creativecommons.org/licenses/by-nc-nd/4.0/
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rights_invalid_str_mv Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)
© 2023 Elsevier B.V. All rights reserved.
https://creativecommons.org/licenses/by-nc-nd/4.0/
http://purl.org/coar/access_right/c_f1cf
eu_rights_str_mv embargoedAccess
dc.format.extent.spa.fl_str_mv 1 página
dc.format.mimetype.spa.fl_str_mv application/pdf
dc.publisher.spa.fl_str_mv Elsevier
dc.publisher.place.spa.fl_str_mv Netherlands
dc.source.spa.fl_str_mv https://www.sciencedirect.com/science/article/abs/pii/S0167732223009091
institution Corporación Universidad de la Costa
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spelling Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)© 2023 Elsevier B.V. All rights reserved.https://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/embargoedAccesshttp://purl.org/coar/access_right/c_f1cfMoussout, Hamou86a59201f0a4715cd9326089c22e2ed1Dehmani, Younes70066b540b24fd6dbb2902efa09923c4Dison S.P., Franco617ef49ebc758ce5201754e858ead2a2600georgin, jordana3cb4434fbc1c630e529d2cddd15f71d4600Daou, Ikram820c5ec33589762e639ed3e35383e18bLamhasni, Taibia1ac98afa62826af0ddf4d70ca73ccb5Ilyas, Chabri2e8a273628f7879167b44c4151c81b74Ahlafi, Hammoubf4a8510d97ed8d2c7ce6bf81d4c3b3bTaky, Mohamed53f8940ebbd83a9bc95e02b61f032cdbShaim, Abdelillah0ad1ef296e6109ccd5a50fde427eeeeeSadik, Abouarnadasse48f0a7b4d584d932f5267153806206ff2023-11-08T21:12:16Z20252023-11-08T21:12:16Z2023Hamou Moussout, Younes Dehmani, Dison S.P. Franco, Jordana Georgin, Ikram Daou, Taibi Lamhasni, Chabri Ilyas, Hammou Ahlafi, Mohamed Taky, Abdelillah Shaim, Abouarnadasse Sadik, Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer, Journal of Molecular Liquids, Volume 383, 2023, 122106, ISSN 0167-7322, https://doi.org/10.1016/j.molliq.2023.1221060167-7322https://hdl.handle.net/11323/1057910.1016/j.molliq.2023.1221061873-3166Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/This work analyzes the adsorption of cadmium, a potentially toxic pollutant, on biopolymers synthesized from shrimp shells, as a promising new adsorbent. Spectroscopic analysis, such as FTIR, ATD/ATG, XRD, and SEM/EDX techniques, were used to characterize chitin before it was exposed to cadmium ions. Experimental data indicate that Cd(II) adsorption proceeds with pseudo-second-order model kinetics and is influenced by increasing temperature. In the equilibrium, the maximum adsorption capacity obtained was 58.82 mg g−1 at a temperature of 308 K. Experiments to obtain adsorption data were performed at T = 298–318 K. The saturated adsorption capacities of Cd(II) range from 57.40 to 59.90 mg g−1. The application of the physics-statistics model indicates that the Cd(II) atoms are adsorbed on the surface of the chitosan forming a monolayer. In addition to that, the results also show that the adsorption affinity increases with the system temperature, resulting in higher affinity and an increase of 30% in the adsorption capacity. The adsorption energy was found to be around 2.5 kJ mol−1, indicating that the adsorption is physical and endothermic. The entropy was found to quickly increases (reaching a maximum value of 6 × 10−22 kJ mol−1 K−1) at low concentrations followed by the equilibrium after the 40 mg L−1, indicating that the equilibrium is quickly reached. The Gibbs free energy indicates that the process is spontaneous (ranging from −1.364 to −1.451 kJ mol−1) and that the energy tends to remain constant after 15 mg L−1. Last, the results indicate that the Cd(II) is adsorbed due to dipole–dipole interactions and possible coordination bounds. The results of tests on the adsorption of cadmium by chitin showed that this biopolymer could replace other more expensive adsorbents.1 páginaapplication/pdfengElsevierNetherlandshttps://www.sciencedirect.com/science/article/abs/pii/S0167732223009091Towards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymerArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/drafthttp://purl.org/coar/version/c_b1a7d7d4d402bcceJournal of Molecular Liquids383CadmiumUptake mechanismChitin biopolymerORIGINALTowards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin biopolymer.pdfTowards an in-depth experimental and theoretical understanding of the cadmium uptake mechanism on a synthesized chitin 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corporada 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.
