2017 |
Castro, O N; Benites, J; Rodilla, J; Santiago, J C; Simirgiotis, M; Sepulveda, B; Areche, C Metabolomic Analysis of the Lichen Everniopsis Trulla Using Ultra High Performance Liquid Chromatography-Quadrupole-Orbitrap Mass Spectrometry (Uhplc-Q-Ot-Ms) Artículo de revista Chromatographia, 80 (6), pp. 967-973, 2017, ISSN: 0009-5893. Resumen | Enlaces | BibTeX | Etiquetas: depsides, depsidones, everniopsis identification lichens, metabolites, orbitrap, secondary trulla, uhplc-esi-ms @article{RN335, title = {Metabolomic Analysis of the Lichen Everniopsis Trulla Using Ultra High Performance Liquid Chromatography-Quadrupole-Orbitrap Mass Spectrometry (Uhplc-Q-Ot-Ms)}, author = { O.N. Castro and J. Benites and J. Rodilla and J.C. Santiago and M. Simirgiotis and B. Sepulveda and C. Areche}, url = {/brokenurl#<Go to ISI>://WOS:000402824400015}, doi = {10.1007/s10337-017-3304-4}, issn = {0009-5893}, year = {2017}, date = {2017-01-01}, journal = {Chromatographia}, volume = {80}, number = {6}, pages = {967-973}, abstract = {A new depside was identified in the methanolic extract from the lichen Everniopsis trulla based on the metabolomics UHPLC-DAD-MS analysis and HESI-MS-MS fragmentation patterns along with thirty-two known compounds for the first time. The compounds were structurally characterized by UV and high resolution quadrupole orbitrap mass spectra and by comparison with literature. According to the characteristic fragmentation patterns, the presence of two simple aromatic compounds, six lipid derivatives, eight depsidones, thirteen depsides, a chromone, two diphenylethers, and a dibenzofuran were identified. To our knowledge, this is the first study of the lichen E. trulla by liquid chromatography hyphenated with tandem mass spectrometry.}, keywords = {depsides, depsidones, everniopsis identification lichens, metabolites, orbitrap, secondary trulla, uhplc-esi-ms}, pubstate = {published}, tppubtype = {article} } A new depside was identified in the methanolic extract from the lichen Everniopsis trulla based on the metabolomics UHPLC-DAD-MS analysis and HESI-MS-MS fragmentation patterns along with thirty-two known compounds for the first time. The compounds were structurally characterized by UV and high resolution quadrupole orbitrap mass spectra and by comparison with literature. According to the characteristic fragmentation patterns, the presence of two simple aromatic compounds, six lipid derivatives, eight depsidones, thirteen depsides, a chromone, two diphenylethers, and a dibenzofuran were identified. To our knowledge, this is the first study of the lichen E. trulla by liquid chromatography hyphenated with tandem mass spectrometry. |
Rojas-Aedo, J F; Gil-Duran, C; Del-Cid, A; Valdes, N; Alamos, P; Vaca, I; Garcia-Rico, R O; Levican, G; Tello, M; Chavez, R The Biosynthetic Gene Cluster for Andrastin a in Penicillium Roqueforti Artículo de revista Frontiers in Microbiology, 8 , 2017, ISSN: 1664-302x. Resumen | Enlaces | BibTeX | Etiquetas: andrastin cells chrysogenum, cluster, fo-3929, fungal gene metabolism, metabolites, penicillium rna-mediated roqueforti, secondary secretion, silencing, strains, transporter @article{RN340, title = {The Biosynthetic Gene Cluster for Andrastin a in Penicillium Roqueforti}, author = { J.F. Rojas-Aedo and C. Gil-Duran and A. Del-Cid and N. Valdes and P. Alamos and I. Vaca and R.O. Garcia-Rico and G. Levican and M. Tello and R. Chavez}, url = {/brokenurl#<Go to ISI>://WOS:000400641200002}, doi = {10.3389/fmicb.2017.00813}, issn = {1664-302x}, year = {2017}, date = {2017-01-01}, journal = {Frontiers in Microbiology}, volume = {8}, abstract = {Penicillium roqueforti is a filamentous fungus involved in the ripening of several kinds of blue cheeses. In addition, this fungus produces several secondary metabolites, including the meroterpenoid compound andrastin A, a promising antitumoral compound. However, to date the genomic cluster responsible for the biosynthesis of this compound in P. roqueforti has not been described. In this work, we have sequenced and annotated a genomic region of approximately 29.4 kbp (named the adr gene cluster) that is involved in the biosynthesis of andrastin A in P. roqueforti. This region contains ten genes, named adrA, adrC, adrD, adrE, adrF, adrG, adrH, adrI, adrJ and adrK. Interestingly, the adrB gene previously found in the adr cluster from P. chrysogenum, was found as a residual pseudogene in the adr cluster from P. roqueforti. RNA-mediated gene silencing of each of the ten genes resulted in significant reductions in andrastin A production, confirming that all of them are involved in the biosynthesis of this compound. Of particular interest was the adrC gene, encoding for a major facilitator superfamily transporter. According to our results, this gene is required for the production of andrastin A but does not have any role in its secretion to the extracellular medium. The identification of the adr cluster in P. roqueforti will be important to understand the molecular basis of the production of andrastin A, and for the obtainment of strains of P. roqueforti overproducing andrastin A that might be of interest for the cheese industry.}, keywords = {andrastin cells chrysogenum, cluster, fo-3929, fungal gene metabolism, metabolites, penicillium rna-mediated roqueforti, secondary secretion, silencing, strains, transporter}, pubstate = {published}, tppubtype = {article} } Penicillium roqueforti is a filamentous fungus involved in the ripening of several kinds of blue cheeses. In addition, this fungus produces several secondary metabolites, including the meroterpenoid compound andrastin A, a promising antitumoral compound. However, to date the genomic cluster responsible for the biosynthesis of this compound in P. roqueforti has not been described. In this work, we have sequenced and annotated a genomic region of approximately 29.4 kbp (named the adr gene cluster) that is involved in the biosynthesis of andrastin A in P. roqueforti. This region contains ten genes, named adrA, adrC, adrD, adrE, adrF, adrG, adrH, adrI, adrJ and adrK. Interestingly, the adrB gene previously found in the adr cluster from P. chrysogenum, was found as a residual pseudogene in the adr cluster from P. roqueforti. RNA-mediated gene silencing of each of the ten genes resulted in significant reductions in andrastin A production, confirming that all of them are involved in the biosynthesis of this compound. Of particular interest was the adrC gene, encoding for a major facilitator superfamily transporter. According to our results, this gene is required for the production of andrastin A but does not have any role in its secretion to the extracellular medium. The identification of the adr cluster in P. roqueforti will be important to understand the molecular basis of the production of andrastin A, and for the obtainment of strains of P. roqueforti overproducing andrastin A that might be of interest for the cheese industry. |
Torrent, C; Gil-Duran, C; Rojas-Aedo, J F; Medina, E; Vaca, I; Castro, P; Garcia-Rico, R O; Cotoras, M; Mendoza, L; Levican, G; Chavez, R Role of Sfk1 Gene in the Filamentous Fungus Penicillium Roqueforti Artículo de revista Frontiers in Microbiology, 8 , 2017, ISSN: 1664-302x. Resumen | Enlaces | BibTeX | Etiquetas: alpha-subunit, biosynthesis, botrytis-cinerea, changes, chrysogenum, expression, four gene germination, growth kinase, metabolites, of pathways, penicillium phenotypic protein rna-mediated roqueforti, saccharomyces-cerevisiae, secondary signaling silencing, stress, suppressor @article{RN338, title = {Role of Sfk1 Gene in the Filamentous Fungus Penicillium Roqueforti}, author = { C. Torrent and C. Gil-Duran and J.F. Rojas-Aedo and E. Medina and I. Vaca and P. Castro and R.O. Garcia-Rico and M. Cotoras and L. Mendoza and G. Levican and R. Chavez}, url = {/brokenurl#<Go to ISI>://WOS:000417142700001}, doi = {10.3389/fmicb.2017.02424}, issn = {1664-302x}, year = {2017}, date = {2017-01-01}, journal = {Frontiers in Microbiology}, volume = {8}, abstract = {The sfk1 (suppressor of four kinase) gene has been mainly studied in Saccharomyces cerevisiae, where it was shown to be involved in growth and thermal stress resistance. This gene is widely conserved within the phylum Ascomycota. Despite this, to date sfk1 has not been studied in any filamentous fungus. Previously, we found that the orthologous of sfk1 was differentially expressed in a strain of Penicillium roqueforti with an altered phenotype. In this work, we have performed a functional characterization of this gene by using RNAi-silencing technology. The silencing of sfk1 in P. roqueforti resulted in decreased apical growth and the promotion of conidial germination, but interesting, it had no effect on conidiation. In addition, the attenuation of the sfk1 expression sensitized the fungus to osmotic stress, but not to thermal stress. RNA-mediated gene-silencing of sfk1 also affected cell wall integrity in the fungus. Finally, the silencing of sfk1 depleted the production of the main secondary metabolites of P. roqueforti, namely roquefortine C, andrastin A, and mycophenolic acid. To the best of our knowledge this is the first study of the sfk1 gene in filamentous fungi.}, keywords = {alpha-subunit, biosynthesis, botrytis-cinerea, changes, chrysogenum, expression, four gene germination, growth kinase, metabolites, of pathways, penicillium phenotypic protein rna-mediated roqueforti, saccharomyces-cerevisiae, secondary signaling silencing, stress, suppressor}, pubstate = {published}, tppubtype = {article} } The sfk1 (suppressor of four kinase) gene has been mainly studied in Saccharomyces cerevisiae, where it was shown to be involved in growth and thermal stress resistance. This gene is widely conserved within the phylum Ascomycota. Despite this, to date sfk1 has not been studied in any filamentous fungus. Previously, we found that the orthologous of sfk1 was differentially expressed in a strain of Penicillium roqueforti with an altered phenotype. In this work, we have performed a functional characterization of this gene by using RNAi-silencing technology. The silencing of sfk1 in P. roqueforti resulted in decreased apical growth and the promotion of conidial germination, but interesting, it had no effect on conidiation. In addition, the attenuation of the sfk1 expression sensitized the fungus to osmotic stress, but not to thermal stress. RNA-mediated gene-silencing of sfk1 also affected cell wall integrity in the fungus. Finally, the silencing of sfk1 depleted the production of the main secondary metabolites of P. roqueforti, namely roquefortine C, andrastin A, and mycophenolic acid. To the best of our knowledge this is the first study of the sfk1 gene in filamentous fungi. |
Torres-Benitez, A; Rivera-Montalvo, M; Sepulveda, B; Castro, O N; Nagles, E; Simirgiotis, M J; Garcia-Beltran, O; Areche, C Metabolomic Analysis of Two Parmotrema Lichens: P-Robustum (Degel.) Hale and P-Andinum (Mull. Arg.) Hale Using Uhplc-Esi-Ot-Ms-Ms Artículo de revista Molecules, 22 (11), 2017, ISSN: 1420-3049. Resumen | Enlaces | BibTeX | Etiquetas: constituents, electrospray, lichens, metabolites, metabolomic, ms/ms, nyl. orbitrap, parmotrema, phenolic-compounds, secondary uhplc-ms-ms @article{RN334, title = {Metabolomic Analysis of Two Parmotrema Lichens: P-Robustum (Degel.) Hale and P-Andinum (Mull. Arg.) Hale Using Uhplc-Esi-Ot-Ms-Ms}, author = { A. Torres-Benitez and M. Rivera-Montalvo and B. Sepulveda and O.N. Castro and E. Nagles and M.J. Simirgiotis and O. Garcia-Beltran and C. Areche}, url = {/brokenurl#<Go to ISI>://WOS:000416528400063}, doi = {10.3390/molecules22111861}, issn = {1420-3049}, year = {2017}, date = {2017-01-01}, journal = {Molecules}, volume = {22}, number = {11}, abstract = {Lichens are symbiotic associations of fungi with microalgae and/or cyanobacteria. Lichens belonging to the Parmeliaceae family comprise 2700 species of lichens, including the Parmotrema genus which is composed of 300 species. The metabolites of this genus include depsides, depsidones, phenolics, polysaccharides, lipids, diphenylethers and dibenzofurans, which are responsible for the biological activities reported including antidiabetic, antihelmintic, anticancer, antioxidant, antibacterial, anti-inflammatory, antimitotic, antitumoral, antifungal, and antioxidant enzyme inhibitory. Due to scarce knowledge of metabolomic profiles of Parmotrema species (P. andinum and P. robustum), a full metabolome study based on ultra-high performance liquid chromatography- diode array detector-electrospray ionization-quadrupole-orbitrap-mass-spectrometry (UHPLC-DAD-ESI-Q-orbitrap MS) was performed for a comprehensive characterization of their substances. From the methanolic extracts of these species, a total of 54 metabolites were identified for the first time using this hyphenated technique, including thirty compounds in P. andinum, and thirty-seven in P. robustum. Moreover, two compounds were not identified as known compounds, and could be new structures, according to our data. This report shows that this technique is effective and accurate for rapid chemical identification of lichen substances and the compounds identified could serve as chemotaxonomic markers to differentiate these ruffle lichens.}, keywords = {constituents, electrospray, lichens, metabolites, metabolomic, ms/ms, nyl. orbitrap, parmotrema, phenolic-compounds, secondary uhplc-ms-ms}, pubstate = {published}, tppubtype = {article} } Lichens are symbiotic associations of fungi with microalgae and/or cyanobacteria. Lichens belonging to the Parmeliaceae family comprise 2700 species of lichens, including the Parmotrema genus which is composed of 300 species. The metabolites of this genus include depsides, depsidones, phenolics, polysaccharides, lipids, diphenylethers and dibenzofurans, which are responsible for the biological activities reported including antidiabetic, antihelmintic, anticancer, antioxidant, antibacterial, anti-inflammatory, antimitotic, antitumoral, antifungal, and antioxidant enzyme inhibitory. Due to scarce knowledge of metabolomic profiles of Parmotrema species (P. andinum and P. robustum), a full metabolome study based on ultra-high performance liquid chromatography- diode array detector-electrospray ionization-quadrupole-orbitrap-mass-spectrometry (UHPLC-DAD-ESI-Q-orbitrap MS) was performed for a comprehensive characterization of their substances. From the methanolic extracts of these species, a total of 54 metabolites were identified for the first time using this hyphenated technique, including thirty compounds in P. andinum, and thirty-seven in P. robustum. Moreover, two compounds were not identified as known compounds, and could be new structures, according to our data. This report shows that this technique is effective and accurate for rapid chemical identification of lichen substances and the compounds identified could serve as chemotaxonomic markers to differentiate these ruffle lichens. |
2015 |
Figueroa, L; Jimenez, C; Rodriguez, J; Areche, C; Chavez, R; Henriquez, M; Cruz, De La M; Diaz, C; Segade, Y; Vaca, I 3-Nitroasterric Acid Derivatives from an Antarctic Sponge-Derived Pseudogymnoascus Sp Fungus Artículo de revista Journal of Natural Products, 78 (4), pp. 919-923, 2015, ISSN: 0163-3864. Resumen | Enlaces | BibTeX | Etiquetas: ascomycete asterric geomyces, metabolites, natural-products @article{RN239, title = {3-Nitroasterric Acid Derivatives from an Antarctic Sponge-Derived Pseudogymnoascus Sp Fungus}, author = { L. Figueroa and C. Jimenez and J. Rodriguez and C. Areche and R. Chavez and M. Henriquez and M. De La Cruz and C. Diaz and Y. Segade and I. Vaca}, url = {/brokenurl#<Go to ISI>://WOS:000353665100042}, doi = {10.1021/np500906k}, issn = {0163-3864}, year = {2015}, date = {2015-01-01}, journal = {Journal of Natural Products}, volume = {78}, number = {4}, pages = {919-923}, abstract = {Four new nitroasterric acid derivatives, pseudogymnoascins A-C (1-3) and 3-nitroasterric acid (4), along with the two known compounds, questin and pyriculamide, were obtained from the cultures of a Pseudogymnoascus sp. fungus isolated from an Antarctic marine sponge belonging to the genus Hymeniacidon. The structures of the new compounds were determined by extensive NMR and MS analyses. These compounds are the first nitro derivatives of the known fungal metabolite asterric acid. Several asterric acid derivatives isolated from other fungal strains have shown antibacterial and antifungal activities. However, the new compounds described in this work were inactive against a panel of bacteria and fungi (MIC > 64 mu g/mL).}, keywords = {ascomycete asterric geomyces, metabolites, natural-products}, pubstate = {published}, tppubtype = {article} } Four new nitroasterric acid derivatives, pseudogymnoascins A-C (1-3) and 3-nitroasterric acid (4), along with the two known compounds, questin and pyriculamide, were obtained from the cultures of a Pseudogymnoascus sp. fungus isolated from an Antarctic marine sponge belonging to the genus Hymeniacidon. The structures of the new compounds were determined by extensive NMR and MS analyses. These compounds are the first nitro derivatives of the known fungal metabolite asterric acid. Several asterric acid derivatives isolated from other fungal strains have shown antibacterial and antifungal activities. However, the new compounds described in this work were inactive against a panel of bacteria and fungi (MIC > 64 mu g/mL). |
2014 |
Henriquez, M; Vergara, K; Norambuena, J; Beiza, A; Maza, F; Ubilla, P; Araya, I; Chavez, R; San-Martin, A; Darias, J; Darias, M J; Vaca, I Diversity of Cultivable Fungi Associated with Antarctic Marine Sponges and Screening for Their Antimicrobial, Antitumoral and Antioxidant Potential Artículo de revista World Journal of Microbiology & Biotechnology, 30 (1), pp. 65-76, 2014, ISSN: 0959-3993. Resumen | Enlaces | BibTeX | Etiquetas: antarctic antimicrobial, antioxidant, antitumoral, bioactive coastal diversity, fungi, geomyces haliclona-simulans, identification, metabolites, microorganisms natural-products, penicillium, phylogenetic sp., sponges, suberites-zeteki, syndrome, waters, white-nose @article{RN180, title = {Diversity of Cultivable Fungi Associated with Antarctic Marine Sponges and Screening for Their Antimicrobial, Antitumoral and Antioxidant Potential}, author = { M. Henriquez and K. Vergara and J. Norambuena and A. Beiza and F. Maza and P. Ubilla and I. Araya and R. Chavez and A. San-Martin and J. Darias and M.J. Darias and I. Vaca}, url = {/brokenurl#<Go to ISI>://WOS:000329248200007}, doi = {10.1007/s11274-013-1418-x}, issn = {0959-3993}, year = {2014}, date = {2014-01-01}, journal = {World Journal of Microbiology & Biotechnology}, volume = {30}, number = {1}, pages = {65-76}, abstract = {The diversity of sponge-associated fungi has been poorly investigated in remote geographical areas like Antarctica. In this study, 101 phenotypically different fungal isolates were obtained from 11 sponge samples collected in King George Island, Antarctica. The analysis of ITS sequences revealed that they belong to the phylum Ascomycota. Sixty-five isolates belong to the genera Geomyces, Penicillium, Epicoccum, Pseudeurotium, Thelebolus, Cladosporium, Aspergillus, Aureobasidium, Phoma, and Trichocladium but 36 isolates could not be identified at genus level. In order to estimate the potential of these isolates as producers of interesting bioactivities, antimicrobial, antitumoral and antioxidant activities of fungal culture extracts were assayed. Around 51 % of the extracts, mainly from the genus Geomyces and non identified relatives, showed antimicrobial activity against some of the bacteria tested. On the other hand, around 42 % of the extracts showed potent antitumoral activity, Geomyces sp. having the best performance. Finally, the potential of the isolated fungi as producers of antioxidant activity seems to be moderate. Our results suggest that fungi associated with Antarctic sponges, particularly Geomyces, would be valuable sources of antimicrobial and antitumoral compounds. To our knowledge, this is the first report describing the biodiversity and the metabolic potential of fungi associated with Antarctic marine sponges.}, keywords = {antarctic antimicrobial, antioxidant, antitumoral, bioactive coastal diversity, fungi, geomyces haliclona-simulans, identification, metabolites, microorganisms natural-products, penicillium, phylogenetic sp., sponges, suberites-zeteki, syndrome, waters, white-nose}, pubstate = {published}, tppubtype = {article} } The diversity of sponge-associated fungi has been poorly investigated in remote geographical areas like Antarctica. In this study, 101 phenotypically different fungal isolates were obtained from 11 sponge samples collected in King George Island, Antarctica. The analysis of ITS sequences revealed that they belong to the phylum Ascomycota. Sixty-five isolates belong to the genera Geomyces, Penicillium, Epicoccum, Pseudeurotium, Thelebolus, Cladosporium, Aspergillus, Aureobasidium, Phoma, and Trichocladium but 36 isolates could not be identified at genus level. In order to estimate the potential of these isolates as producers of interesting bioactivities, antimicrobial, antitumoral and antioxidant activities of fungal culture extracts were assayed. Around 51 % of the extracts, mainly from the genus Geomyces and non identified relatives, showed antimicrobial activity against some of the bacteria tested. On the other hand, around 42 % of the extracts showed potent antitumoral activity, Geomyces sp. having the best performance. Finally, the potential of the isolated fungi as producers of antioxidant activity seems to be moderate. Our results suggest that fungi associated with Antarctic sponges, particularly Geomyces, would be valuable sources of antimicrobial and antitumoral compounds. To our knowledge, this is the first report describing the biodiversity and the metabolic potential of fungi associated with Antarctic marine sponges. |
2013 |
Reinoso, R; Cajas-Madriaga, D; Martinez, M; Martin, San A; Perez, C; Fajardo, V; Becerra, J Biological Activity of Macromycetes Isolated from Chilean Subantarctic Ecosystems Artículo de revista Journal of the Chilean Chemical Society, 58 (4), pp. 2016-2019, 2013, ISSN: 0717-9707. Resumen | Enlaces | BibTeX | Etiquetas: activity, alkaloids and antibacterial, antifungal ecosystems, fungi, metabolites, secondary subantarctic @article{RN112, title = {Biological Activity of Macromycetes Isolated from Chilean Subantarctic Ecosystems}, author = { R. Reinoso and D. Cajas-Madriaga and M. Martinez and A. San Martin and C. Perez and V. Fajardo and J. Becerra}, url = {/brokenurl#<Go to ISI>://WOS:000331238800020}, doi = {10.4067/S0717-97072013000400024}, issn = {0717-9707}, year = {2013}, date = {2013-01-01}, journal = {Journal of the Chilean Chemical Society}, volume = {58}, number = {4}, pages = {2016-2019}, abstract = {Twenty six compounds were identified by GC-MS analysis from culture broth of six Macromycetes growing in subantarctic forests in southern Chile: Mycena hialinotricha, Collybia butyracea, Inocybe geophylla, Entoloma nubigenum, Stropharia semiglobata and Psathyrella sp. Antifungal and antibacterial activity were evaluated through agar diffusion test. This assay showed bioactivity against Penicillium notatum, Fusarium oxysporum, Rhyzoctonia solani, Ceratocistys pilifera, Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli, Escherichia faecalis and Staphilococcus aureus.}, keywords = {activity, alkaloids and antibacterial, antifungal ecosystems, fungi, metabolites, secondary subantarctic}, pubstate = {published}, tppubtype = {article} } Twenty six compounds were identified by GC-MS analysis from culture broth of six Macromycetes growing in subantarctic forests in southern Chile: Mycena hialinotricha, Collybia butyracea, Inocybe geophylla, Entoloma nubigenum, Stropharia semiglobata and Psathyrella sp. Antifungal and antibacterial activity were evaluated through agar diffusion test. This assay showed bioactivity against Penicillium notatum, Fusarium oxysporum, Rhyzoctonia solani, Ceratocistys pilifera, Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli, Escherichia faecalis and Staphilococcus aureus. |
Diaz, C; Garcia, C; Iturriaga-Vasquez, P; Aguirre, M J; Muena, J P; Contreras, R; Ormazabal-Toledo, R; Isaacs, M Experimental and Theoretical Study on the Oxidation Mechanism of Dopamine in N-Octyl Pyridinium Based Ionic Liquids-Carbon Paste Modified Electrodes Artículo de revista Electrochimica Acta, 111 , pp. 846-854, 2013, ISSN: 0013-4686. Resumen | Enlaces | BibTeX | Etiquetas: behavior, detection, disk dopamine electrochemical electrode, electrodes, impedance impedance, insights, ionic liquids-carbon mechanism, metabolites, oxidation paste rat rotating separation, spectroscopy, striatum @article{RN129, title = {Experimental and Theoretical Study on the Oxidation Mechanism of Dopamine in N-Octyl Pyridinium Based Ionic Liquids-Carbon Paste Modified Electrodes}, author = { C. Diaz and C. Garcia and P. Iturriaga-Vasquez and M.J. Aguirre and J.P. Muena and R. Contreras and R. Ormazabal-Toledo and M. Isaacs}, url = {/brokenurl#<Go to ISI>://WOS:000329531100111}, doi = {10.1016/j.electacta.2013.08.103}, issn = {0013-4686}, year = {2013}, date = {2013-01-01}, journal = {Electrochimica Acta}, volume = {111}, pages = {846-854}, publisher = {2013 Elsevier Ltd.}, abstract = {This work describes the influence of n-octyl pyridinium cations based ionicliquids-carbon paste modified electrodes on the oxidation mechanism of dopamine. Ionic liquids formed by hexafluorophosphate anion and n-octyl pyridinium [R-OPy](+); R= CH3, H, CF3, where ionic liquids containing CH3 and CF3 are new products, were synthesized and characterized. Modified carbon paste electrodes with these salts were characterized by electrochemicalimpedance spectroscopy and cyclic voltammetry. Electrochemical oxidation of dopamine was studied in PBS buffer solution at pH = 7.4. The influence of the ionic liquids in the oxidation of dopamine was studied by cyclic voltammetry and rotating disk electrode. The results show that typical carbon paste electrode presents an electrochemical/chemical mechanism; whereas [OPy]PF6 and [CF3-OPy]PF6 modified electrodes present an electrochemical/chemical/electrochemical mechanism. The experimental study is complemented with a theoretical analysis of substituent effects in terms of the molecular electrostatic potential, Mulliken population analysis and second order perturbation theory probed at the cation moiety of the IL These indices consistently show an electron density accumulation at the ipso position of the pyridinium moiety of the IL that is in agreement with the electrochemical characterization.}, keywords = {behavior, detection, disk dopamine electrochemical electrode, electrodes, impedance impedance, insights, ionic liquids-carbon mechanism, metabolites, oxidation paste rat rotating separation, spectroscopy, striatum}, pubstate = {published}, tppubtype = {article} } This work describes the influence of n-octyl pyridinium cations based ionicliquids-carbon paste modified electrodes on the oxidation mechanism of dopamine. Ionic liquids formed by hexafluorophosphate anion and n-octyl pyridinium [R-OPy](+); R= CH3, H, CF3, where ionic liquids containing CH3 and CF3 are new products, were synthesized and characterized. Modified carbon paste electrodes with these salts were characterized by electrochemicalimpedance spectroscopy and cyclic voltammetry. Electrochemical oxidation of dopamine was studied in PBS buffer solution at pH = 7.4. The influence of the ionic liquids in the oxidation of dopamine was studied by cyclic voltammetry and rotating disk electrode. The results show that typical carbon paste electrode presents an electrochemical/chemical mechanism; whereas [OPy]PF6 and [CF3-OPy]PF6 modified electrodes present an electrochemical/chemical/electrochemical mechanism. The experimental study is complemented with a theoretical analysis of substituent effects in terms of the molecular electrostatic potential, Mulliken population analysis and second order perturbation theory probed at the cation moiety of the IL These indices consistently show an electron density accumulation at the ipso position of the pyridinium moiety of the IL that is in agreement with the electrochemical characterization. |