Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization

Graphene oxide/polypyrrole (GO/PPy) composite material was prepared to explore its utility in the removal of diclofenac from aqueous system. The characterization was achieved using Fourier transform infrared spectroscopy, X-ray powder diffraction analysis, thermogravimetry-differential thermal analy...

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Autores:
Rahman, Nafisur
Raheem, Abdur
Nasir, Mohd
Franco, Dison
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:11323/14074
Acceso en línea:
https://hdl.handle.net/11323/14074
https://repositorio.cuc.edu.co/
Palabra clave:
Graphene oxide/polypyrrole composite
Diclofenac
Sorption
Central composite design
Fractal-like kinetics
Rights
openAccess
License
Atribución 4.0 Internacional (CC BY 4.0)
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oai_identifier_str oai:repositorio.cuc.edu.co:11323/14074
network_acronym_str RCUC2
network_name_str REDICUC - Repositorio CUC
repository_id_str
dc.title.eng.fl_str_mv Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization
title Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization
spellingShingle Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization
Graphene oxide/polypyrrole composite
Diclofenac
Sorption
Central composite design
Fractal-like kinetics
title_short Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization
title_full Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization
title_fullStr Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization
title_full_unstemmed Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization
title_sort Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization
dc.creator.fl_str_mv Rahman, Nafisur
Raheem, Abdur
Nasir, Mohd
Franco, Dison
dc.contributor.author.none.fl_str_mv Rahman, Nafisur
Raheem, Abdur
Nasir, Mohd
Franco, Dison
dc.subject.proposal.eng.fl_str_mv Graphene oxide/polypyrrole composite
Diclofenac
Sorption
Central composite design
Fractal-like kinetics
topic Graphene oxide/polypyrrole composite
Diclofenac
Sorption
Central composite design
Fractal-like kinetics
description Graphene oxide/polypyrrole (GO/PPy) composite material was prepared to explore its utility in the removal of diclofenac from aqueous system. The characterization was achieved using Fourier transform infrared spectroscopy, X-ray powder diffraction analysis, thermogravimetry-differential thermal analyses, scanning electron microscopy coupled with energy dispersive X-ray analysis and transmission electron microscopy analysis. Response surface methodology was exploited to optimize the process variables for the sorption of diclofenac onto GO/PPy. Three variables such as contact time, adsorbent dose and initial concentration of diclofenac were selected for optimization to achieve maximum removal of diclofenac. All experiments were conducted at pH 5. The contact time, adsorbent dose and initial concentration of diclofenac were examined in the ranges of 03–37 min, 13–147 mg/25 mL and 10–110 mg/L, respectively. The optimum values obtained were: contact time: 20 min; GO/PPy dose: 80 mg/25 mL and initial diclofenac concentration: 60 mg/L. The maximum sorption capacity and percent removal of diclofenac were found to be 29.50 mg/g and 98.50 %, respectively. The measured data (at equilibrium) were investigated using different isotherm models and best described by Freundlich model (R2 = 0.9943–0.9952, χ2 = 0.0062–0.0077, APE = 1.45–1.61). The experimental kinetic data were analyzed with the help of fractal-like kinetic models. The kinetic data are best fitted by fractal-like mixed 1,2 order (R2 = 0.9830–0.9886, χ2 = 0.0014–0.0036, APE = 0.6780–1.1059). Adsorption mechanism has been discussed based on kinetic, FTIR and molecular docking studies which indicated the participation of π-π interactions and hydrogen bonding on energetically heterogeneous surface. The adsorption/desorption test demonstrated that GO/PPy had excellent reusability performance up to 15 cycles.
publishDate 2023
dc.date.issued.none.fl_str_mv 2023-08-22
dc.date.accessioned.none.fl_str_mv 2025-04-04T14:45:38Z
dc.date.available.none.fl_str_mv 2025-04-04T14:45:38Z
dc.type.none.fl_str_mv Artículo de revista
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dc.identifier.citation.none.fl_str_mv Nafisur Rahman, Abdur Raheem, Mohd Nasir, Dison S.P. Franco, Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization, Diamond and Related Materials, Volume 139, 2023, 110328, ISSN 0925-9635, https://doi.org/10.1016/j.diamond.2023.110328.
dc.identifier.issn.none.fl_str_mv 0925-9635
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/11323/14074
dc.identifier.doi.none.fl_str_mv 10.1016/j.diamond.2023.110328.
dc.identifier.instname.none.fl_str_mv Corporación Universidad de la Costa
dc.identifier.reponame.none.fl_str_mv REDICUC - Repositorio CUC
dc.identifier.repourl.none.fl_str_mv https://repositorio.cuc.edu.co/
identifier_str_mv Nafisur Rahman, Abdur Raheem, Mohd Nasir, Dison S.P. Franco, Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization, Diamond and Related Materials, Volume 139, 2023, 110328, ISSN 0925-9635, https://doi.org/10.1016/j.diamond.2023.110328.
0925-9635
10.1016/j.diamond.2023.110328.
Corporación Universidad de la Costa
REDICUC - Repositorio CUC
url https://hdl.handle.net/11323/14074
https://repositorio.cuc.edu.co/
dc.language.iso.none.fl_str_mv eng
language eng
dc.relation.ispartofjournal.none.fl_str_mv Diamond and Related Materials
dc.relation.references.none.fl_str_mv K. Kummerer, Resistant in the environment, J. Antimicrob. Chemother. 54 (2004) 311–320
N.N. Koopaei, M. Abdollahi, Health risk associated with pharmaceuticals in wastewater, DARU J. Pharma. Sci. 25 (2017) 9–15
A. Carucci, G. Cappai, M. Piredda, Biodegradability and toxicity of pharmaceuticals in biological wastewater treatment plants, J. Environ. Sci. Health Part A 41 (2006) 1831–1842
J. Kołodziejska, M. Kołodziejczyk, Diclofenac in the treatment of pain in patients with rheumatic diseases, Reumatologia 3 (2018) 174–183
D.D. Shah, Z.H. Sorathia, Tramadol/diclofenac fixed-dose combination: a review of its use in severe acute pain, Pain Ther. 9 (2020) 113–128
P. Sathishkumar, R.A.A. Meena, T. Paanisami, V. Ashokkumar, T. Palvannan, F. L. Gu, Occurrence, interactive effects and ecological risk of diclofenac in environmental compartments and biota - a review, Sci. Total Environ. (2020), https://doi.org/10.1016/j.scitotenv.2019.134057
A.J. Ebele, M.A. Abdallah, S. Harrad, Pharmaceuticals and personal care products (PPCPs) in the fresh water aquatic environment, Emer. Contam. 3 (2017) 1–16
R. Green, I. Newton, S. Shultz, A.A. Cunningham, M. Gilbert, D.J. Pain, V. Prakashr, Diclofenac poisoning as a cause of vulture population declines across the Indian subcontinent, J. Appl. Ecol. 41 (2004) 793–800
N.J. Efosa, W. Kleiner, W. Kloas, F. Hoffmann, Diclofenac can exhibit estrogenic modes of action in male Xenopus laevis, and affects the hypothalamuspituitarygonad axis and mating vocalizations, Chemosphere 173 (2017) 69–77
A.C. Mehinto, E.M. Hill, C.R. Tyler, Uptake and biological effects of environmentally relevant concentrations of the nonsteroidal anti-inflammatory pharmaceutical diclofenac in rainbow trout (Oncorhynchus mykiss), Environ. Sci. Technol. 44 (2010) 2176–2182
P. De Voogt, M.L. Janex-Habibi, F. Sacher, L. Puijker, M. Mons, Development of a common priority list of pharmaceuticals relevant for the water cycle, Water Sci. Technol. 59 (2009) 39–46
K. Vella, Commission Implementing Decision (EU) 2015/495, 2015
N. Mao, L. Huang, Q. Shuai, Facile synthesis of porous carbon for the removal of diclofenac sodium from water, ACS Omega 4 (2019) 15051–15060
J. Wang, S. Wang, Removal of pharmaceuticals and personal care products (PPCPs) from wastewater: a review, J. Environ. Manag. 182 (2016) 620–640
A. Khan, M. Anwar, Advance techniques for diclofenac removal from pharmaceutical wastewater: a review, Int. Res. J. Adv. Sci. HUB 2 (2020) 26–31
H. Pourzamani, N. Mengelizadeh, Y. Hajizadeh, H. Mohammadi, Electrochemical degradation of diclofenac using three-dimensional electrode reactor with multiwalled carbon nanotibes, Environ. Sci. Pollut. Res. 25 (2018) 24746–24763
K. Kowalska, G. Maniakova, M. Carotenuto, O. Sacco, V. Vaiano, G. Lofrano, L. Rizzo, Removal of carbamazepine, diclofenac and trimethoprim by solar driven advanced oxidation processes in a compound triangular collector based reactor: a comparison between homogeneous and heterogeneous processes, Chemosphere (2020), https://doi.org/10.1016/j.chemosphere.2019.124665
T.P. Nguyen, Q.B. Tran, Q.V. Ly, L.T. Hai, D.T. Le, M.B. Tran, T.T.T. Ho, X. C. Nguyen, M. Shokouhimehr, D.-V.N. Vo, S.S. Lam, H.-T. Do, S.Y. Kim, T. V. Tungand, Q.V. Le, Enhanced visible photocatalytic degradation of diclofenac over N-doped TiO2 assisted with H2O2: a kinetic and pathway study, Arab. J. Chem. 13 (2020) 8361–8371
I.B. Ivshina, E.A. Tyumina, M.V. Kuzmina, E.V. Vikhareva, Features of diclofenac biodegradation by Rhodococcus ruber IEGM 346, Sci. Rep. (2019), https://doi.org/ 10.1038/s41598-019-45732-9
F.P. Ghavi, F. Raouf, A.D. Koohi, A review on diclofenac removal from aqueous solution, emphasizing on adsorption method, Iran. J. Chem. Chem. Eng. 39 (2020) 141–154
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spelling Atribución 4.0 Internacional (CC BY 4.0)© 2023 Elsevier B.V.https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Rahman, NafisurRaheem, AbdurNasir, MohdFranco, Disonvirtual::989-12025-04-04T14:45:38Z2025-04-04T14:45:38Z2023-08-22Nafisur Rahman, Abdur Raheem, Mohd Nasir, Dison S.P. Franco, Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimization, Diamond and Related Materials, Volume 139, 2023, 110328, ISSN 0925-9635, https://doi.org/10.1016/j.diamond.2023.110328.0925-9635https://hdl.handle.net/11323/1407410.1016/j.diamond.2023.110328.Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/Graphene oxide/polypyrrole (GO/PPy) composite material was prepared to explore its utility in the removal of diclofenac from aqueous system. The characterization was achieved using Fourier transform infrared spectroscopy, X-ray powder diffraction analysis, thermogravimetry-differential thermal analyses, scanning electron microscopy coupled with energy dispersive X-ray analysis and transmission electron microscopy analysis. Response surface methodology was exploited to optimize the process variables for the sorption of diclofenac onto GO/PPy. Three variables such as contact time, adsorbent dose and initial concentration of diclofenac were selected for optimization to achieve maximum removal of diclofenac. All experiments were conducted at pH 5. The contact time, adsorbent dose and initial concentration of diclofenac were examined in the ranges of 03–37 min, 13–147 mg/25 mL and 10–110 mg/L, respectively. The optimum values obtained were: contact time: 20 min; GO/PPy dose: 80 mg/25 mL and initial diclofenac concentration: 60 mg/L. The maximum sorption capacity and percent removal of diclofenac were found to be 29.50 mg/g and 98.50 %, respectively. The measured data (at equilibrium) were investigated using different isotherm models and best described by Freundlich model (R2 = 0.9943–0.9952, χ2 = 0.0062–0.0077, APE = 1.45–1.61). The experimental kinetic data were analyzed with the help of fractal-like kinetic models. The kinetic data are best fitted by fractal-like mixed 1,2 order (R2 = 0.9830–0.9886, χ2 = 0.0014–0.0036, APE = 0.6780–1.1059). Adsorption mechanism has been discussed based on kinetic, FTIR and molecular docking studies which indicated the participation of π-π interactions and hydrogen bonding on energetically heterogeneous surface. The adsorption/desorption test demonstrated that GO/PPy had excellent reusability performance up to 15 cycles.15 páginasapplication/pdfengElsevier B.V.Netherlandshttps://linkinghub.elsevier.com/retrieve/pii/S0925963523006532Fractal-like kinetic modelling for sorption of diclofenac onto graphene oxide/polypyrrole composite: Mechanism analysis and response surface methodology for optimizationArtículo 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_970fb48d4fbd8a85Diamond and Related MaterialsK. Kummerer, Resistant in the environment, J. Antimicrob. Chemother. 54 (2004) 311–320N.N. Koopaei, M. Abdollahi, Health risk associated with pharmaceuticals in wastewater, DARU J. Pharma. Sci. 25 (2017) 9–15A. Carucci, G. Cappai, M. Piredda, Biodegradability and toxicity of pharmaceuticals in biological wastewater treatment plants, J. Environ. Sci. Health Part A 41 (2006) 1831–1842J. Kołodziejska, M. Kołodziejczyk, Diclofenac in the treatment of pain in patients with rheumatic diseases, Reumatologia 3 (2018) 174–183D.D. Shah, Z.H. Sorathia, Tramadol/diclofenac fixed-dose combination: a review of its use in severe acute pain, Pain Ther. 9 (2020) 113–128P. Sathishkumar, R.A.A. Meena, T. Paanisami, V. Ashokkumar, T. Palvannan, F. L. Gu, Occurrence, interactive effects and ecological risk of diclofenac in environmental compartments and biota - a review, Sci. Total Environ. (2020), https://doi.org/10.1016/j.scitotenv.2019.134057A.J. Ebele, M.A. Abdallah, S. Harrad, Pharmaceuticals and personal care products (PPCPs) in the fresh water aquatic environment, Emer. Contam. 3 (2017) 1–16R. Green, I. Newton, S. Shultz, A.A. Cunningham, M. Gilbert, D.J. Pain, V. Prakashr, Diclofenac poisoning as a cause of vulture population declines across the Indian subcontinent, J. Appl. Ecol. 41 (2004) 793–800N.J. Efosa, W. Kleiner, W. Kloas, F. Hoffmann, Diclofenac can exhibit estrogenic modes of action in male Xenopus laevis, and affects the hypothalamuspituitarygonad axis and mating vocalizations, Chemosphere 173 (2017) 69–77A.C. Mehinto, E.M. Hill, C.R. Tyler, Uptake and biological effects of environmentally relevant concentrations of the nonsteroidal anti-inflammatory pharmaceutical diclofenac in rainbow trout (Oncorhynchus mykiss), Environ. Sci. Technol. 44 (2010) 2176–2182P. De Voogt, M.L. Janex-Habibi, F. Sacher, L. Puijker, M. Mons, Development of a common priority list of pharmaceuticals relevant for the water cycle, Water Sci. Technol. 59 (2009) 39–46K. Vella, Commission Implementing Decision (EU) 2015/495, 2015N. Mao, L. Huang, Q. Shuai, Facile synthesis of porous carbon for the removal of diclofenac sodium from water, ACS Omega 4 (2019) 15051–15060J. Wang, S. Wang, Removal of pharmaceuticals and personal care products (PPCPs) from wastewater: a review, J. Environ. Manag. 182 (2016) 620–640A. Khan, M. Anwar, Advance techniques for diclofenac removal from pharmaceutical wastewater: a review, Int. Res. J. Adv. Sci. HUB 2 (2020) 26–31H. Pourzamani, N. Mengelizadeh, Y. Hajizadeh, H. Mohammadi, Electrochemical degradation of diclofenac using three-dimensional electrode reactor with multiwalled carbon nanotibes, Environ. Sci. Pollut. Res. 25 (2018) 24746–24763K. Kowalska, G. Maniakova, M. Carotenuto, O. Sacco, V. Vaiano, G. Lofrano, L. Rizzo, Removal of carbamazepine, diclofenac and trimethoprim by solar driven advanced oxidation processes in a compound triangular collector based reactor: a comparison between homogeneous and heterogeneous processes, Chemosphere (2020), https://doi.org/10.1016/j.chemosphere.2019.124665T.P. Nguyen, Q.B. Tran, Q.V. Ly, L.T. Hai, D.T. Le, M.B. Tran, T.T.T. Ho, X. C. Nguyen, M. Shokouhimehr, D.-V.N. Vo, S.S. Lam, H.-T. Do, S.Y. Kim, T. V. Tungand, Q.V. Le, Enhanced visible photocatalytic degradation of diclofenac over N-doped TiO2 assisted with H2O2: a kinetic and pathway study, Arab. J. Chem. 13 (2020) 8361–8371I.B. Ivshina, E.A. Tyumina, M.V. Kuzmina, E.V. Vikhareva, Features of diclofenac biodegradation by Rhodococcus ruber IEGM 346, Sci. Rep. (2019), https://doi.org/ 10.1038/s41598-019-45732-9F.P. Ghavi, F. Raouf, A.D. Koohi, A review on diclofenac removal from aqueous solution, emphasizing on adsorption method, Iran. J. Chem. Chem. 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 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.</li>
      <li>
        Para evitar toda confusión, el Licenciante aclara que, cuando la obra es una composición musical:
        <ol type="i">
          <li>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.</li>
          <li>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.</li>
        </ol>
      </li>
      <li>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.</li>
    </ol>
  </li>
  <br/>
  <li>
    Representaciones, Garantías y Limitaciones de Responsabilidad.
    <p>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.</p>
  </li>
  <br/>
  <li>
    Limitación de responsabilidad.
    <p>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.</p>
  </li>
  <br/>
  <li>
    Término.
    <ol type="a">
      <li>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.</li>
      <li>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.</li>
    </ol>
  </li>
  <br/>
  <li>
    Varios.
    <ol type="a">
      <li>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.</li>
      <li>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.</li>
      <li>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.</li>
      <li>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.</li>
    </ol>
  </li>
  <br/>
</ol>
