RATIONALE: Sauroxine and N-demethylsauroxine are lycodine-type Lycopodium alkaloids. In recent ye... more RATIONALE: Sauroxine and N-demethylsauroxine are lycodine-type Lycopodium alkaloids. In recent years, Lycopodium alkaloids have gained significant interest due to their unique skeletal characteristics as well as due to their acetylcholinesterase activity. It is known that drugs that inhibit acetylcholinesterase can be used to treat the early stages of Alzheimer's disease. METHODS: Sauroxine and N-demethylsauroxine were isolated from the aerial parts of Huperzia saururus (Lam.) Trevis. Electron ionization mass spectrometry (EI-MS) (low resolution) and collision-induced dissociation tandem mass spectrometry (CID-MS/MS) fragmentation was conducted using an ion trap, GCQ Plus mass spectrometer with MS/MS. Electron ionization high-resolution mass spectrometry (EI-HRMS) was performed in a magnetic sector mass spectrometer (Micromass VG). RESULTS: Using GC/EI-CID-MS/MS we obtained different fragmentation routes that connect all the ionic populations. In addition, the use of EI-HRMS allowed us to measure the exact masses of all the fragment ions, and, with all this information gathered, we tried to establish a fragmentation scheme concordant with the ascendant and descendant species. CONCLUSIONS: The mass spectrometry studies presented in this work complete our mass studies of Lycopodium alkaloids. The mass spectrometry work presented has been very useful to confirm the structures as well as to support the biogenetic relationships between the lycodine-type Lycopodium alkaloids: sauroxine and N-demethylsauroxine.
Acacia caven (Mol.) Molina pollen proteases. Application to the peptide synthesis and to laundry detergents. (2009). Cristina Barcia, Evelina Quiroga, Carlos Ardanaz, Gustavo Quiroga, Sonia Barberis. In: Biochemical Engineering. Series: Biotechnology in Agriculture, Industry and Medicine (Fabián ...
Mass spectrometry and theoretical calculations about the loss of Methyl radical from methoxilated coumarins
Journal of Molecular Structure, 2015
ABSTRACT In this study we have performed CID mass spectrometry measurements and theoretical calcu... more ABSTRACT In this study we have performed CID mass spectrometry measurements and theoretical calculations in a selected series of coumarins. Our theoretical and experimental results indicate that there is room for reasonable doubts about the fragmentation way previously proposed by Shapiro and Djerassi (1965). A complementary explanation about the fragmentation way of the methyl loss from methoxy coumarins has been reported in this work. Our results demonstrated that different theoretical models are very useful to explain the fragmentation occurred in MS, supporting the usual rules of fragmentation. Although the QTAIM analysis gives a good correlation in order to explain the formation of p-quinoid resonance forms; however, the best correlation has been obtained using the NBO approximation as well as from the Wiberg indexes.
In addition to the known mulinolic and mulinenic acids, two diterpenoids, mulin-11-ene-13-a,14-a-... more In addition to the known mulinolic and mulinenic acids, two diterpenoids, mulin-11-ene-13-a,14-a-dihydroxy-20-oic and mulin-12-ene-14-one-20-oic acids, were isolated from the aerial parts of Mulinum spinosum (Cav.) Pers. (Apiaceae). Their structures were determined based on spectroscopic studies. #
Sauroxine and N-demethylsauroxine are lycodine-type Lycopodium alkaloids. In recent years, Lycopo... more Sauroxine and N-demethylsauroxine are lycodine-type Lycopodium alkaloids. In recent years, Lycopodium alkaloids have gained significant interest due to their unique skeletal characteristics as well as due to their acetylcholinesterase activity. It is known that drugs that inhibit acetylcholinesterase can be used to treat the early stages of Alzheimer's disease. Sauroxine and N-demethylsauroxine were isolated from the aerial parts of Huperzia saururus (Lam.) Trevis. Electron ionization mass spectrometry (EI-MS) (low resolution) and collision-induced dissociation tandem mass spectrometry (CID-MS/MS) fragmentation was conducted using an ion trap, GCQ Plus mass spectrometer with MS/MS. Electron ionization high-resolution mass spectrometry (EI-HRMS) was performed in a magnetic sector mass spectrometer (Micromass VG). Using GC/EI-CID-MS/MS we obtained different fragmentation routes that connect all the ionic populations. In addition, the use of EI-HRMS allowed us to measure the exact masses of all the fragment ions, and, with all this information gathered, we tried to establish a fragmentation scheme concordant with the ascendant and descendant species. The mass spectrometry studies presented in this work complete our mass studies of Lycopodium alkaloids. The mass spectrometry work presented has been very useful to confirm the structures as well as to support the biogenetic relationships between the lycodine-type Lycopodium alkaloids: sauroxine and N-demethylsauroxine.
The electron impact induced fragmentations of seven methoxynaphthoflavones have been studied with... more The electron impact induced fragmentations of seven methoxynaphthoflavones have been studied with the aid of low- and high-resolution measurements, metastable decompositions and isotope labelling using carbon-13 atoms. The retro Diels-Alder cleavage of the methoxynaphthoflavones is strongly influenced by the substituent position providing in most cases intact A- and B-ring fragments. The intensity ratio of these ring fragments appears to be very sensitive to the charge distribution within the parent ion. Copyright -Copyright 1999 John Wiley & Sons, Ltd.
Allelochemical effects were observed when Tribolium castaneum (Herbst) adults were treated with B... more Allelochemical effects were observed when Tribolium castaneum (Herbst) adults were treated with Baccharis salicifolia (Ruiz & Pavon) Pers essential oil. The main biological activities were toxicity and repellence. Terpenes present in the essential oil were identified by GC-MS, and some authentic samples were tested to assess their activity individually. The most acutely toxic compounds after 3 days were β-pinene and pulegone. Most of the monoterpenes elicited symptoms indicative of neurotoxicity. The most repellent compound was α-terpineol. Toxic and repellent effects of chemical derivatives of the major sesquiterpene present in B salicifolia essential oil, as well as a series of monoterpenes, were evaluated in order to investigate structure-activity relationships. The reduced derivatives of the monoterpenes and sesquiterpenes were more repellent that their carbonyl analogues. In addition, unsaturation in the germacrane skeleton enhanced repellent activity.
Allelochemical effects were observed when Tribolium castaneum (Herbst) adults were treated with B... more Allelochemical effects were observed when Tribolium castaneum (Herbst) adults were treated with Baccharis salicifolia (Ruiz & Pavon) Pers essential oil. The main biological activities were toxicity and repellence. Terpenes present in the essential oil were identified by GC-MS, and some authentic samples were tested to assess their activity individually. The most acutely toxic compounds after 3 days were beta-pinene and pulegone. Most of the monoterpenes elicited symptoms indicative of neurotoxicity. The most repellent compound was alpha-terpineol. Toxic and repellent effects of chemical derivatives of the major sesquiterpene present in B salicifolia essential oil, as well as a series of monoterpenes, were evaluated in order to investigate structure-activity relationships. The reduced derivatives of the monoterpenes and sesquiterpenes were more repellent that their carbonyl analogues. In addition, unsaturation in the germacrane skeleton enhanced repellent activity.
Bioconversion of Ilicic Alcohol and Derivatives with Cultures of Filamentous Fungi
Natural Product Letters, 2002
Aspergillus niger cultures monohydroxylate ilicic alcohol in C-3 in a cis position with respect t... more Aspergillus niger cultures monohydroxylate ilicic alcohol in C-3 in a cis position with respect to the methyl groups at C-4 and C-10, and trans position with respect to the hydroxyl group of C-4. Furthermore, Aspergillus niger cultures reduce ilicic aldehyde to its corresponding alcohol.
The essential oil of the aerial parts of Baccharis salicifolia was examined by GC and GC-MS and t... more The essential oil of the aerial parts of Baccharis salicifolia was examined by GC and GC-MS and the major components were identified as α-pinene, camphene, β-pinene, α-phellandrene, α-cubebene, β-cariophyllene, 6,9-guaiadiene, germacrene D and germacrone. The essential oil was tested against eight Gram positive and Gram negative bacteria. The essential oil was found to exhibit moderate antibacterial activity against Gram positive bacteria tested with MIC values from 0.47 to 0.94 (µg/ml).
Coumarin Dihydrocoumarin Hydroxycoumarin Metabolism a b s t r a c t Coumarin metabolism by severa... more Coumarin Dihydrocoumarin Hydroxycoumarin Metabolism a b s t r a c t Coumarin metabolism by several Aspergillus strains was studied. Aspergillus ochraceus and Aspergillus niger carried out the reduction of the C3eC4 double bond to yield dihydrocoumarin in 24 h. Meanwhile, the first strain did not transform dihydrocoumarin after 7 d, A. niger demonstrated to have two divergent catabolic pathways: (a) the lactone moiety opening and further reduction of the carboxylic acid furnishing the primary alcohol 2-(3-hydroxypropyl)phenol and, (b) the hydroxylation of the aromatic ring of dihydrocoumarin at a specific position to give 6-hydroxy-3,4-dihydrochromen-2-one. Aspergillus flavus did not perform double bond reductions, and only produced oxygenated metabolites, mainly 5-hydroxycoumarin. Enzyme-specific inhibitors and a coumarin analogous were useful to confirm the A. niger catabolic route.
Flourensia oolepis Blake (Asteraceae) essential oil had a complex chemical composition with t-muu... more Flourensia oolepis Blake (Asteraceae) essential oil had a complex chemical composition with t-muurolene (6.14%), santolinetriene (6.22%), 2-methylene-4,8,8-trimethyl-4-vinyl-bicyclo[5.2.0]nonane (10.15%), d-cadinene (10.27%) and g-gurjunene (20.69%) comprising more than 50% of the oil. This oil had repellent and toxic effects on Tribolium castaneum Herbst (Coleoptera: Tenebrionidae) adults, acting as a contact toxin. Myzus persicae (Sulzer) (Homoptera: Aphididae) and Leptinotarsa decemlineata Say (Coleoptera: Chrysomelidae) adults showed behavioral sensibility to this oil.
RATIONALE: Sauroxine and N-demethylsauroxine are lycodine-type Lycopodium alkaloids. In recent ye... more RATIONALE: Sauroxine and N-demethylsauroxine are lycodine-type Lycopodium alkaloids. In recent years, Lycopodium alkaloids have gained significant interest due to their unique skeletal characteristics as well as due to their acetylcholinesterase activity. It is known that drugs that inhibit acetylcholinesterase can be used to treat the early stages of Alzheimer's disease. METHODS: Sauroxine and N-demethylsauroxine were isolated from the aerial parts of Huperzia saururus (Lam.) Trevis. Electron ionization mass spectrometry (EI-MS) (low resolution) and collision-induced dissociation tandem mass spectrometry (CID-MS/MS) fragmentation was conducted using an ion trap, GCQ Plus mass spectrometer with MS/MS. Electron ionization high-resolution mass spectrometry (EI-HRMS) was performed in a magnetic sector mass spectrometer (Micromass VG). RESULTS: Using GC/EI-CID-MS/MS we obtained different fragmentation routes that connect all the ionic populations. In addition, the use of EI-HRMS allowed us to measure the exact masses of all the fragment ions, and, with all this information gathered, we tried to establish a fragmentation scheme concordant with the ascendant and descendant species. CONCLUSIONS: The mass spectrometry studies presented in this work complete our mass studies of Lycopodium alkaloids. The mass spectrometry work presented has been very useful to confirm the structures as well as to support the biogenetic relationships between the lycodine-type Lycopodium alkaloids: sauroxine and N-demethylsauroxine.
Acacia caven (Mol.) Molina pollen proteases. Application to the peptide synthesis and to laundry detergents. (2009). Cristina Barcia, Evelina Quiroga, Carlos Ardanaz, Gustavo Quiroga, Sonia Barberis. In: Biochemical Engineering. Series: Biotechnology in Agriculture, Industry and Medicine (Fabián ...
Mass spectrometry and theoretical calculations about the loss of Methyl radical from methoxilated coumarins
Journal of Molecular Structure, 2015
ABSTRACT In this study we have performed CID mass spectrometry measurements and theoretical calcu... more ABSTRACT In this study we have performed CID mass spectrometry measurements and theoretical calculations in a selected series of coumarins. Our theoretical and experimental results indicate that there is room for reasonable doubts about the fragmentation way previously proposed by Shapiro and Djerassi (1965). A complementary explanation about the fragmentation way of the methyl loss from methoxy coumarins has been reported in this work. Our results demonstrated that different theoretical models are very useful to explain the fragmentation occurred in MS, supporting the usual rules of fragmentation. Although the QTAIM analysis gives a good correlation in order to explain the formation of p-quinoid resonance forms; however, the best correlation has been obtained using the NBO approximation as well as from the Wiberg indexes.
In addition to the known mulinolic and mulinenic acids, two diterpenoids, mulin-11-ene-13-a,14-a-... more In addition to the known mulinolic and mulinenic acids, two diterpenoids, mulin-11-ene-13-a,14-a-dihydroxy-20-oic and mulin-12-ene-14-one-20-oic acids, were isolated from the aerial parts of Mulinum spinosum (Cav.) Pers. (Apiaceae). Their structures were determined based on spectroscopic studies. #
Sauroxine and N-demethylsauroxine are lycodine-type Lycopodium alkaloids. In recent years, Lycopo... more Sauroxine and N-demethylsauroxine are lycodine-type Lycopodium alkaloids. In recent years, Lycopodium alkaloids have gained significant interest due to their unique skeletal characteristics as well as due to their acetylcholinesterase activity. It is known that drugs that inhibit acetylcholinesterase can be used to treat the early stages of Alzheimer's disease. Sauroxine and N-demethylsauroxine were isolated from the aerial parts of Huperzia saururus (Lam.) Trevis. Electron ionization mass spectrometry (EI-MS) (low resolution) and collision-induced dissociation tandem mass spectrometry (CID-MS/MS) fragmentation was conducted using an ion trap, GCQ Plus mass spectrometer with MS/MS. Electron ionization high-resolution mass spectrometry (EI-HRMS) was performed in a magnetic sector mass spectrometer (Micromass VG). Using GC/EI-CID-MS/MS we obtained different fragmentation routes that connect all the ionic populations. In addition, the use of EI-HRMS allowed us to measure the exact masses of all the fragment ions, and, with all this information gathered, we tried to establish a fragmentation scheme concordant with the ascendant and descendant species. The mass spectrometry studies presented in this work complete our mass studies of Lycopodium alkaloids. The mass spectrometry work presented has been very useful to confirm the structures as well as to support the biogenetic relationships between the lycodine-type Lycopodium alkaloids: sauroxine and N-demethylsauroxine.
The electron impact induced fragmentations of seven methoxynaphthoflavones have been studied with... more The electron impact induced fragmentations of seven methoxynaphthoflavones have been studied with the aid of low- and high-resolution measurements, metastable decompositions and isotope labelling using carbon-13 atoms. The retro Diels-Alder cleavage of the methoxynaphthoflavones is strongly influenced by the substituent position providing in most cases intact A- and B-ring fragments. The intensity ratio of these ring fragments appears to be very sensitive to the charge distribution within the parent ion. Copyright -Copyright 1999 John Wiley & Sons, Ltd.
Allelochemical effects were observed when Tribolium castaneum (Herbst) adults were treated with B... more Allelochemical effects were observed when Tribolium castaneum (Herbst) adults were treated with Baccharis salicifolia (Ruiz & Pavon) Pers essential oil. The main biological activities were toxicity and repellence. Terpenes present in the essential oil were identified by GC-MS, and some authentic samples were tested to assess their activity individually. The most acutely toxic compounds after 3 days were β-pinene and pulegone. Most of the monoterpenes elicited symptoms indicative of neurotoxicity. The most repellent compound was α-terpineol. Toxic and repellent effects of chemical derivatives of the major sesquiterpene present in B salicifolia essential oil, as well as a series of monoterpenes, were evaluated in order to investigate structure-activity relationships. The reduced derivatives of the monoterpenes and sesquiterpenes were more repellent that their carbonyl analogues. In addition, unsaturation in the germacrane skeleton enhanced repellent activity.
Allelochemical effects were observed when Tribolium castaneum (Herbst) adults were treated with B... more Allelochemical effects were observed when Tribolium castaneum (Herbst) adults were treated with Baccharis salicifolia (Ruiz & Pavon) Pers essential oil. The main biological activities were toxicity and repellence. Terpenes present in the essential oil were identified by GC-MS, and some authentic samples were tested to assess their activity individually. The most acutely toxic compounds after 3 days were beta-pinene and pulegone. Most of the monoterpenes elicited symptoms indicative of neurotoxicity. The most repellent compound was alpha-terpineol. Toxic and repellent effects of chemical derivatives of the major sesquiterpene present in B salicifolia essential oil, as well as a series of monoterpenes, were evaluated in order to investigate structure-activity relationships. The reduced derivatives of the monoterpenes and sesquiterpenes were more repellent that their carbonyl analogues. In addition, unsaturation in the germacrane skeleton enhanced repellent activity.
Bioconversion of Ilicic Alcohol and Derivatives with Cultures of Filamentous Fungi
Natural Product Letters, 2002
Aspergillus niger cultures monohydroxylate ilicic alcohol in C-3 in a cis position with respect t... more Aspergillus niger cultures monohydroxylate ilicic alcohol in C-3 in a cis position with respect to the methyl groups at C-4 and C-10, and trans position with respect to the hydroxyl group of C-4. Furthermore, Aspergillus niger cultures reduce ilicic aldehyde to its corresponding alcohol.
The essential oil of the aerial parts of Baccharis salicifolia was examined by GC and GC-MS and t... more The essential oil of the aerial parts of Baccharis salicifolia was examined by GC and GC-MS and the major components were identified as α-pinene, camphene, β-pinene, α-phellandrene, α-cubebene, β-cariophyllene, 6,9-guaiadiene, germacrene D and germacrone. The essential oil was tested against eight Gram positive and Gram negative bacteria. The essential oil was found to exhibit moderate antibacterial activity against Gram positive bacteria tested with MIC values from 0.47 to 0.94 (µg/ml).
Coumarin Dihydrocoumarin Hydroxycoumarin Metabolism a b s t r a c t Coumarin metabolism by severa... more Coumarin Dihydrocoumarin Hydroxycoumarin Metabolism a b s t r a c t Coumarin metabolism by several Aspergillus strains was studied. Aspergillus ochraceus and Aspergillus niger carried out the reduction of the C3eC4 double bond to yield dihydrocoumarin in 24 h. Meanwhile, the first strain did not transform dihydrocoumarin after 7 d, A. niger demonstrated to have two divergent catabolic pathways: (a) the lactone moiety opening and further reduction of the carboxylic acid furnishing the primary alcohol 2-(3-hydroxypropyl)phenol and, (b) the hydroxylation of the aromatic ring of dihydrocoumarin at a specific position to give 6-hydroxy-3,4-dihydrochromen-2-one. Aspergillus flavus did not perform double bond reductions, and only produced oxygenated metabolites, mainly 5-hydroxycoumarin. Enzyme-specific inhibitors and a coumarin analogous were useful to confirm the A. niger catabolic route.
Flourensia oolepis Blake (Asteraceae) essential oil had a complex chemical composition with t-muu... more Flourensia oolepis Blake (Asteraceae) essential oil had a complex chemical composition with t-muurolene (6.14%), santolinetriene (6.22%), 2-methylene-4,8,8-trimethyl-4-vinyl-bicyclo[5.2.0]nonane (10.15%), d-cadinene (10.27%) and g-gurjunene (20.69%) comprising more than 50% of the oil. This oil had repellent and toxic effects on Tribolium castaneum Herbst (Coleoptera: Tenebrionidae) adults, acting as a contact toxin. Myzus persicae (Sulzer) (Homoptera: Aphididae) and Leptinotarsa decemlineata Say (Coleoptera: Chrysomelidae) adults showed behavioral sensibility to this oil.
Uploads
Papers by Carlos Ardanaz