2017 |
Nett, R S; Montanares, M; Marcassa, A; Lul, X; Nagel, R; Charles, T C; Hedden, P; Rojas, M C; Peters, R J Elucidation of Gibberellin Biosynthesis in Bacteria Reveals Convergent Evolution Artículo de revista Nature Chemical Biology, 13 (1), pp. 69-74, 2017, ISSN: 1552-4450. Resumen | Enlaces | BibTeX | Etiquetas: artemisinin biosynthesis, bradyrhizobium-japonicum, cloning, cytochrome-p450 ent-kaurene, fungi, gene-cluster, green-revolution, identification, plants, rearrangement @article{RN347, title = {Elucidation of Gibberellin Biosynthesis in Bacteria Reveals Convergent Evolution}, author = { R.S. Nett and M. Montanares and A. Marcassa and X. Lul and R. Nagel and T.C. Charles and P. Hedden and M.C. Rojas and R.J. Peters}, url = {/brokenurl#<Go to ISI>://WOS:000393267200015}, doi = {10.1038/Nchembio.2232}, issn = {1552-4450}, year = {2017}, date = {2017-01-01}, journal = {Nature Chemical Biology}, volume = {13}, number = {1}, pages = {69-74}, abstract = {Gibberellins (GAs) are crucial phytohormones involved in many aspects of plant growth and development, including plant-microbe interactions, which has led to GA production by plant-associated fungi and bacteria as well. While the GA biosynthetic pathways in plants and fungi have been elucidated and found to have arisen independently through convergent evolution, little has been uncovered about GA biosynthesis in bacteria. Some nitrogen-fixing, symbiotic, legume-associated rhizobia, including Bradyrhizobium japonicum-the symbiont of soybean and Sinorhizobium fredii-a broad-host-nodulating species-contain a putative GA biosynthetic operon, or gene cluster. Through functional characterization of five unknown genes, we demonstrate that this operon encodes the enzymes necessary to produce GA(9), thereby elucidating bacterial GA biosynthesis. The distinct nature of these enzymes indicates that bacteria have independently evolved a third biosynthetic pathway for GA production. Furthermore, our results also reveal a central biochemical logic that is followed in all three convergently evolved GA biosynthetic pathways.}, keywords = {artemisinin biosynthesis, bradyrhizobium-japonicum, cloning, cytochrome-p450 ent-kaurene, fungi, gene-cluster, green-revolution, identification, plants, rearrangement}, pubstate = {published}, tppubtype = {article} } Gibberellins (GAs) are crucial phytohormones involved in many aspects of plant growth and development, including plant-microbe interactions, which has led to GA production by plant-associated fungi and bacteria as well. While the GA biosynthetic pathways in plants and fungi have been elucidated and found to have arisen independently through convergent evolution, little has been uncovered about GA biosynthesis in bacteria. Some nitrogen-fixing, symbiotic, legume-associated rhizobia, including Bradyrhizobium japonicum-the symbiont of soybean and Sinorhizobium fredii-a broad-host-nodulating species-contain a putative GA biosynthetic operon, or gene cluster. Through functional characterization of five unknown genes, we demonstrate that this operon encodes the enzymes necessary to produce GA(9), thereby elucidating bacterial GA biosynthesis. The distinct nature of these enzymes indicates that bacteria have independently evolved a third biosynthetic pathway for GA production. Furthermore, our results also reveal a central biochemical logic that is followed in all three convergently evolved GA biosynthetic pathways. |
2016 |
Gallardo-Fuentes, S; Contreras, R; Ormazabal-Toledo, R Origins of the Anrorc Reactivity in Nitroimidazole Derivatives Artículo de revista Rsc Advances, 6 (30), pp. 25215-25221, 2016, ISSN: 2046-2069. Resumen | Enlaces | BibTeX | Etiquetas: aryne distortions, electrophilicity, methylhydrazine, rearrangement, regioselectivities, rules @article{RN329, title = {Origins of the Anrorc Reactivity in Nitroimidazole Derivatives}, author = { S. Gallardo-Fuentes and R. Contreras and R. Ormazabal-Toledo}, url = {/brokenurl#<Go to ISI>://WOS:000372252700049}, doi = {10.1039/c6ra00199h}, issn = {2046-2069}, year = {2016}, date = {2016-01-01}, journal = {Rsc Advances}, volume = {6}, number = {30}, pages = {25215-25221}, abstract = {The mechanism of the ANRORC-like ring transformation of nitroimidazole derivatives towards aniline has been studied by fully exploring the potential energy surface (PES). For this purpose the reaction of some aniline derivatives towards 1,4-dinitro-1H-imidazole, 2-methyl-1,4-dinitro-1H-imidazole and 5-methyl1,4-dinitro-1H-imidazole and have been employed as model reactions. The study reveals that the most favorable path involves an initial amine attack at the C(5)-C(4) bond of the imidazole moiety, where the imidazole distortion appears to be the main factor for the favored nucleophilic attack on the C(5) site. We further show that the reaction regioselectivity is independent of the substitution patterns on the aryl moiety. Next, we highlight the keywords role of the proton transfer along the reaction pathway of the title reactions to allow a successful connection between two energetically lower regions along the PES: an electrophilically activated ring-opening step followed by the favored 5-exo-trig cyclization. Additionally, we show that this 5-exo-trig cyclization step is the rate determining step. Finally the tether strain and steric effects present in the rate determining TS structure are evaluated by means of the distortion/interaction model.}, keywords = {aryne distortions, electrophilicity, methylhydrazine, rearrangement, regioselectivities, rules}, pubstate = {published}, tppubtype = {article} } The mechanism of the ANRORC-like ring transformation of nitroimidazole derivatives towards aniline has been studied by fully exploring the potential energy surface (PES). For this purpose the reaction of some aniline derivatives towards 1,4-dinitro-1H-imidazole, 2-methyl-1,4-dinitro-1H-imidazole and 5-methyl1,4-dinitro-1H-imidazole and have been employed as model reactions. The study reveals that the most favorable path involves an initial amine attack at the C(5)-C(4) bond of the imidazole moiety, where the imidazole distortion appears to be the main factor for the favored nucleophilic attack on the C(5) site. We further show that the reaction regioselectivity is independent of the substitution patterns on the aryl moiety. Next, we highlight the keywords role of the proton transfer along the reaction pathway of the title reactions to allow a successful connection between two energetically lower regions along the PES: an electrophilically activated ring-opening step followed by the favored 5-exo-trig cyclization. Additionally, we show that this 5-exo-trig cyclization step is the rate determining step. Finally the tether strain and steric effects present in the rate determining TS structure are evaluated by means of the distortion/interaction model. |
2017 |
Elucidation of Gibberellin Biosynthesis in Bacteria Reveals Convergent Evolution Artículo de revista Nature Chemical Biology, 13 (1), pp. 69-74, 2017, ISSN: 1552-4450. |
2016 |
Origins of the Anrorc Reactivity in Nitroimidazole Derivatives Artículo de revista Rsc Advances, 6 (30), pp. 25215-25221, 2016, ISSN: 2046-2069. |