RESUMEN
Mycenarubinâ C, a previously unknown red pyrroloquinoline alkaloid, was isolated from fruiting bodies of the mushroom Mycena rosea and its structure was elucidated mainly by NMR spectroscopy and mass spectrometry. Unlike mycenarubinâ A, the major pyrroloquinoline alkaloid in fruiting bodies of M.â rosea, mycenarubinâ C, contains an eight-membered ring with an additional C1 unit that is hitherto unprecedented for pyrroloquinoline alkaloids known in nature. Incubation of mycenarubinâ A with an excess of formaldehyde revealed that mycenarubinâ C was generated nearly quantitatively from mycenarubinâ A. An investigation into the formaldehyde content of fresh fruiting bodies of M.â rosea showed the presence of considerable amounts of formaldehyde, with values of 5â µg per gram of fresh weight in fresh fruiting bodies. Although mycenarubinâ C did not show bioactivity against selected bacteria and fungi, formaldehyde inhibits the growth of the mycoparasite Spinellus fusiger at concentrations present in fruiting bodies of M.â rosea. Therefore, formaldehyde might play an ecological role in the chemical defence of M.â rosea against S.â fusiger. In turn, S.â fusiger produces gallic acid-presumably to detoxify formaldehyde by reaction of this aldehyde with amino acids and gallic acid to Mannich adducts.
Asunto(s)
Agaricales/química , Alcaloides/farmacología , Formaldehído/farmacología , Cuerpos Fructíferos de los Hongos/química , Mucorales/efectos de los fármacos , Pirroles/farmacología , Quinolinas/farmacología , Agaricales/inmunología , Agaricales/metabolismo , Alcaloides/biosíntesis , Aminoácidos/metabolismo , Antibiosis , Formaldehído/metabolismo , Cuerpos Fructíferos de los Hongos/inmunología , Cuerpos Fructíferos de los Hongos/metabolismo , Ácido Gálico/metabolismo , Inactivación Metabólica/fisiología , Espectroscopía de Resonancia Magnética , Estructura Molecular , Mucorales/metabolismo , Pirroles/metabolismo , Quinolinas/metabolismoRESUMEN
The effect of particle size on the asymmetric catalytic properties of supported ligand-functionalized nanoparticles (NPs) was investigated for the first time and found to alter significantly the activity but surprisingly not the stereoselectivity. These results suggest that the stereoselectivity of these complex systems is primarily determined by the ligand-reactant interaction, whereas the activity is determined by the particle size.