Transition metal doping for improving the fluorescence response of paralytic shellfish poisoning toxins upon pre-chromatographic derivatization

<p>Paralytic shellfish toxins can be quantified in bivalves by the AOAC-2005 method. This method is sensitive for several toxins, but other toxins suffer from strong matrix effects or fluorescence partitioning by multiple oxidation products, reducing their sensitivity. Metals were assessed as...

ver descrição completa

Na minha lista:
Detalhes bibliográficos
Autor principal: Paulo Vale (13163899) (author)
Publicado em: 2025
Assuntos:
Tags: Adicionar Tag
Sem tags, seja o primeiro a adicionar uma tag!
_version_ 1849927644307521536
author Paulo Vale (13163899)
author_facet Paulo Vale (13163899)
author_role author
dc.creator.none.fl_str_mv Paulo Vale (13163899)
dc.date.none.fl_str_mv 2025-11-24T15:40:05Z
dc.identifier.none.fl_str_mv 10.6084/m9.figshare.30695684.v1
dc.relation.none.fl_str_mv https://figshare.com/articles/presentation/Transition_metal_doping_for_improving_the_fluorescence_response_of_paralytic_shellfish_poisoning_toxins_upon_pre-chromatographic_derivatization/30695684
dc.rights.none.fl_str_mv CC BY 4.0
info:eu-repo/semantics/openAccess
dc.subject.none.fl_str_mv Biochemistry
Medicine
Microbiology
Genetics
Molecular Biology
Neuroscience
Biotechnology
Cancer
Inorganic Chemistry
Infectious Diseases
Chemical Sciences not elsewhere classified
Saxitoxins
prechromatographic derivatization
transition metals
paralytic shellfish poisoning
matrix suppression
dc.title.none.fl_str_mv Transition metal doping for improving the fluorescence response of paralytic shellfish poisoning toxins upon pre-chromatographic derivatization
dc.type.none.fl_str_mv Text
Presentation
info:eu-repo/semantics/publishedVersion
text
description <p>Paralytic shellfish toxins can be quantified in bivalves by the AOAC-2005 method. This method is sensitive for several toxins, but other toxins suffer from strong matrix effects or fluorescence partitioning by multiple oxidation products, reducing their sensitivity. Metals were assessed as candidate catalysts to improve the oxidation reactions, instead of the oyster matrix modifier prescribed in this method. The N1-H sub-group of toxins exhibited increased fluorescence upon doping with iron sulphate. The increase was inversely proportional to the fluorescence reduction caused by matrix suppression. Iron acted as a catalyst, lowering the activation energy of the reaction, which otherwise required heating to achieve a similar boost in the fluorescence yield. The fluorescence due to the N1-hydroxyl sub-group of toxins GTX1 + 4 and GTX6 increased with zinc but decreased with iron. When doping with a metal solution fraction-2 of the carboxylic acid partitioning, both metals reduced the fluorescence, while the eluent (NaCL 0.05 M) enhanced it. As metals are retained by COOH cartridges, sulphonic acid leachables might contribute to this reduction. The reduction observed for GTX1 + 4 was primarily due to the decrease in the proportion of the secondary peak over the primary oxidation peak, which can be reversed by doping with an oyster matrix. Nickel chloride was able to replace the oyster modifier effectively in all five bivalve matrices tested, while zinc chloride was not similarly effective. For dcNEO spiked in several bivalve matrices, adding an oyster modifier derived from <i>Magallana gigas</i> caused a 16-19% reduction in fluorescence. Doping with several metals could not achieve the same fluorescence as doping with 0.1 mM acetic acid. For NEO, with one particular oyster extract, the yield could be higher than using NiCl<sub>2</sub>. Depending on the specific oyster extract, the use of the matrix modifier required in the method might not be adequate.</p>
eu_rights_str_mv openAccess
id Manara_dff2f9d2a138be270788bf5616589e12
identifier_str_mv 10.6084/m9.figshare.30695684.v1
network_acronym_str Manara
network_name_str ManaraRepo
oai_identifier_str oai:figshare.com:article/30695684
publishDate 2025
repository.mail.fl_str_mv
repository.name.fl_str_mv
repository_id_str
rights_invalid_str_mv CC BY 4.0
spelling Transition metal doping for improving the fluorescence response of paralytic shellfish poisoning toxins upon pre-chromatographic derivatizationPaulo Vale (13163899)BiochemistryMedicineMicrobiologyGeneticsMolecular BiologyNeuroscienceBiotechnologyCancerInorganic ChemistryInfectious DiseasesChemical Sciences not elsewhere classifiedSaxitoxinsprechromatographic derivatizationtransition metalsparalytic shellfish poisoningmatrix suppression<p>Paralytic shellfish toxins can be quantified in bivalves by the AOAC-2005 method. This method is sensitive for several toxins, but other toxins suffer from strong matrix effects or fluorescence partitioning by multiple oxidation products, reducing their sensitivity. Metals were assessed as candidate catalysts to improve the oxidation reactions, instead of the oyster matrix modifier prescribed in this method. The N1-H sub-group of toxins exhibited increased fluorescence upon doping with iron sulphate. The increase was inversely proportional to the fluorescence reduction caused by matrix suppression. Iron acted as a catalyst, lowering the activation energy of the reaction, which otherwise required heating to achieve a similar boost in the fluorescence yield. The fluorescence due to the N1-hydroxyl sub-group of toxins GTX1 + 4 and GTX6 increased with zinc but decreased with iron. When doping with a metal solution fraction-2 of the carboxylic acid partitioning, both metals reduced the fluorescence, while the eluent (NaCL 0.05 M) enhanced it. As metals are retained by COOH cartridges, sulphonic acid leachables might contribute to this reduction. The reduction observed for GTX1 + 4 was primarily due to the decrease in the proportion of the secondary peak over the primary oxidation peak, which can be reversed by doping with an oyster matrix. Nickel chloride was able to replace the oyster modifier effectively in all five bivalve matrices tested, while zinc chloride was not similarly effective. For dcNEO spiked in several bivalve matrices, adding an oyster modifier derived from <i>Magallana gigas</i> caused a 16-19% reduction in fluorescence. Doping with several metals could not achieve the same fluorescence as doping with 0.1 mM acetic acid. For NEO, with one particular oyster extract, the yield could be higher than using NiCl<sub>2</sub>. Depending on the specific oyster extract, the use of the matrix modifier required in the method might not be adequate.</p>2025-11-24T15:40:05ZTextPresentationinfo:eu-repo/semantics/publishedVersiontext10.6084/m9.figshare.30695684.v1https://figshare.com/articles/presentation/Transition_metal_doping_for_improving_the_fluorescence_response_of_paralytic_shellfish_poisoning_toxins_upon_pre-chromatographic_derivatization/30695684CC BY 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/306956842025-11-24T15:40:05Z
spellingShingle Transition metal doping for improving the fluorescence response of paralytic shellfish poisoning toxins upon pre-chromatographic derivatization
Paulo Vale (13163899)
Biochemistry
Medicine
Microbiology
Genetics
Molecular Biology
Neuroscience
Biotechnology
Cancer
Inorganic Chemistry
Infectious Diseases
Chemical Sciences not elsewhere classified
Saxitoxins
prechromatographic derivatization
transition metals
paralytic shellfish poisoning
matrix suppression
status_str publishedVersion
title Transition metal doping for improving the fluorescence response of paralytic shellfish poisoning toxins upon pre-chromatographic derivatization
title_full Transition metal doping for improving the fluorescence response of paralytic shellfish poisoning toxins upon pre-chromatographic derivatization
title_fullStr Transition metal doping for improving the fluorescence response of paralytic shellfish poisoning toxins upon pre-chromatographic derivatization
title_full_unstemmed Transition metal doping for improving the fluorescence response of paralytic shellfish poisoning toxins upon pre-chromatographic derivatization
title_short Transition metal doping for improving the fluorescence response of paralytic shellfish poisoning toxins upon pre-chromatographic derivatization
title_sort Transition metal doping for improving the fluorescence response of paralytic shellfish poisoning toxins upon pre-chromatographic derivatization
topic Biochemistry
Medicine
Microbiology
Genetics
Molecular Biology
Neuroscience
Biotechnology
Cancer
Inorganic Chemistry
Infectious Diseases
Chemical Sciences not elsewhere classified
Saxitoxins
prechromatographic derivatization
transition metals
paralytic shellfish poisoning
matrix suppression