Phenothiazines solution complexity - determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°C

The ionization constants (pKa) and the pH-dependent solubility (log S-pH) of six phenothiazine derivatives (promazine hydrochloride, chlorpromazine hydrochloride, triflupromazine hydrochloride, fluphenazine dihydrochloride, perphenazine free base, and trifluoperazine dihydrochloride) were determined...

Descripción completa

Detalles Bibliográficos
Autores: Pobudkowska, Aneta, Ràfols Llach, Clara, Subirats i Vila, Xavier, Bosch, Elisabeth, Avdeef, Alex
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2016
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/101994
Acceso en línea:https://hdl.handle.net/2445/101994
Access Level:acceso abierto
Palabra clave:Solubilitat
Química de superfícies
Agents tensioactius
Solubility
Surface chemistry
Surface active agents
id ES_a2e95d61fe012ba4c63c04e4d63f313d
oai_identifier_str oai:recercat.cat:2445/101994
network_acronym_str ES
network_name_str España
repository_id_str
spelling Phenothiazines solution complexity - determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°CPobudkowska, AnetaRàfols Llach, ClaraSubirats i Vila, XavierBosch, ElisabethAvdeef, AlexSolubilitatQuímica de superfíciesAgents tensioactiusSolubilitySurface chemistrySurface active agentsThe ionization constants (pKa) and the pH-dependent solubility (log S-pH) of six phenothiazine derivatives (promazine hydrochloride, chlorpromazine hydrochloride, triflupromazine hydrochloride, fluphenazine dihydrochloride, perphenazine free base, and trifluoperazine dihydrochloride) were determined at 25 and 37 °C. The pKa values of these low-soluble surface active molecules were determined by the cosolvent method (n-propanol/water at 37 °C and methanol/water at 25 °C). The log S-pH profiles were measured at 24 h incubation time in 0.15 M phosphate buffers. The log S-pH "shape-template" method, which critically depends on accurate pKa values (determined independently of solubility data), was used to propose speciation models, which were subsequently refined by rigorous mass-action weighted regression procedure described recently. Differential scanning calorimetry (DSC), UV-visible spectrophotometry, potentiometric, and high performance liquid chromatography (HPLC) measurements were used to characterize the compounds. The intrinsic solubility (S0) values of the three least-soluble drugs (chlorpromazine·HCl, triflupromazine·HCl, and trifluoperazine·2HCl) at 25 °C were 0.5, 1.1, and 2.7 μg/mL (resp.). These values increased to 5.5, 9.2, and 8.7 μg/mL (resp.) at the physiological temperature. The enthalpies of solution for the latter compounds were exceptionally high positive (endothermic) values (99-152 kJ·mol− 1). Cationic sub-micellar aggregates were evident (from the distortions in the log S-pH profiles) for chlorpromazine, fluphenazine, perphenazine, and trifluoperazine at 25 °C. The effects persisted at 37 °C for chlorpromazine and trifluoperazine. The solids in suspension were apparently amorphous in cases where the drugs were introduced as the chloride salts.Elsevier B.V.2016201720162016info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion14 p.application/pdfhttps://hdl.handle.net/2445/101994Articles publicats en revistes (Enginyeria Química i Química Analítica)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: http://dx.doi.org/10.1016/j.ejps.2016.07.013European Journal of Pharmaceutical Sciences, 2016, vol. 93, p. 163-176http://dx.doi.org/10.1016/j.ejps.2016.07.013cc-by-nc-nd (c) Elsevier B.V., 2016http://creativecommons.org/licenses/by-nc-nd/3.0/esinfo:eu-repo/semantics/openAccessoai:recercat.cat:2445/1019942026-05-29T05:05:01Z
dc.title.none.fl_str_mv Phenothiazines solution complexity - determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°C
title Phenothiazines solution complexity - determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°C
spellingShingle Phenothiazines solution complexity - determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°C
Pobudkowska, Aneta
Solubilitat
Química de superfícies
Agents tensioactius
Solubility
Surface chemistry
Surface active agents
title_short Phenothiazines solution complexity - determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°C
title_full Phenothiazines solution complexity - determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°C
title_fullStr Phenothiazines solution complexity - determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°C
title_full_unstemmed Phenothiazines solution complexity - determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°C
title_sort Phenothiazines solution complexity - determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°C
dc.creator.none.fl_str_mv Pobudkowska, Aneta
Ràfols Llach, Clara
Subirats i Vila, Xavier
Bosch, Elisabeth
Avdeef, Alex
author Pobudkowska, Aneta
author_facet Pobudkowska, Aneta
Ràfols Llach, Clara
Subirats i Vila, Xavier
Bosch, Elisabeth
Avdeef, Alex
author_role author
author2 Ràfols Llach, Clara
Subirats i Vila, Xavier
Bosch, Elisabeth
Avdeef, Alex
author2_role author
author
author
author
dc.subject.none.fl_str_mv Solubilitat
Química de superfícies
Agents tensioactius
Solubility
Surface chemistry
Surface active agents
topic Solubilitat
Química de superfícies
Agents tensioactius
Solubility
Surface chemistry
Surface active agents
description The ionization constants (pKa) and the pH-dependent solubility (log S-pH) of six phenothiazine derivatives (promazine hydrochloride, chlorpromazine hydrochloride, triflupromazine hydrochloride, fluphenazine dihydrochloride, perphenazine free base, and trifluoperazine dihydrochloride) were determined at 25 and 37 °C. The pKa values of these low-soluble surface active molecules were determined by the cosolvent method (n-propanol/water at 37 °C and methanol/water at 25 °C). The log S-pH profiles were measured at 24 h incubation time in 0.15 M phosphate buffers. The log S-pH "shape-template" method, which critically depends on accurate pKa values (determined independently of solubility data), was used to propose speciation models, which were subsequently refined by rigorous mass-action weighted regression procedure described recently. Differential scanning calorimetry (DSC), UV-visible spectrophotometry, potentiometric, and high performance liquid chromatography (HPLC) measurements were used to characterize the compounds. The intrinsic solubility (S0) values of the three least-soluble drugs (chlorpromazine·HCl, triflupromazine·HCl, and trifluoperazine·2HCl) at 25 °C were 0.5, 1.1, and 2.7 μg/mL (resp.). These values increased to 5.5, 9.2, and 8.7 μg/mL (resp.) at the physiological temperature. The enthalpies of solution for the latter compounds were exceptionally high positive (endothermic) values (99-152 kJ·mol− 1). Cationic sub-micellar aggregates were evident (from the distortions in the log S-pH profiles) for chlorpromazine, fluphenazine, perphenazine, and trifluoperazine at 25 °C. The effects persisted at 37 °C for chlorpromazine and trifluoperazine. The solids in suspension were apparently amorphous in cases where the drugs were introduced as the chloride salts.
publishDate 2016
dc.date.none.fl_str_mv 2016
2016
2016
2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/101994
url https://hdl.handle.net/2445/101994
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: http://dx.doi.org/10.1016/j.ejps.2016.07.013
European Journal of Pharmaceutical Sciences, 2016, vol. 93, p. 163-176
http://dx.doi.org/10.1016/j.ejps.2016.07.013
dc.rights.none.fl_str_mv cc-by-nc-nd (c) Elsevier B.V., 2016
http://creativecommons.org/licenses/by-nc-nd/3.0/es
info:eu-repo/semantics/openAccess
rights_invalid_str_mv cc-by-nc-nd (c) Elsevier B.V., 2016
http://creativecommons.org/licenses/by-nc-nd/3.0/es
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 14 p.
application/pdf
dc.publisher.none.fl_str_mv Elsevier B.V.
publisher.none.fl_str_mv Elsevier B.V.
dc.source.none.fl_str_mv Articles publicats en revistes (Enginyeria Química i Química Analítica)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869415336489517056
score 15.811543