Heterogeneous catalysts have been synthesized by the conjugation of Hoveyda-Grubbs second-generation catalyst with a lipase. The catalytic properties of the organometallic compound in solution were firstly optimized, evaluating the activity of Ru in the ring-closing metathesis of diethyldiallymalonate at 25 • C at different solvents and in the presence of different additives. The best result was found using tetrahydrofuran as a solvent. Some additives such as phenylboronic acid or polyetheneglycol slightly improved the activity of the Ru catalyst whereas others, such as pyridine or dipeptides affected it negatively. The organometallic compound immobilized on functionalized-surface materials activated with boronic acid or epoxy groups (around 50-60 µg per mg support) and showed 50% conversion at 24 h in the ring-closing metathesis. Cross-linked enzyme aggregates (CLEA's) of the Hoveyda-Grubbs second-generation catalyst with Candida antarctica lipase (CAL-B) were prepared, although low Ru catalyst was found to be translated in low conversion. Therefore, a sol-gel preparation of the Hoveyda-Grubbs second-generation and CAL-B was performed. This catalyst exhibited good activity in the metathesis of diethyldiallymalonate in toluene and in aqueous media. Finally, a new sustainable approach was used by the conjugation lipase-Grubbs in solid phase in aqueous media. Two strategies were used: one using lipase previously covalently immobilized on an epoxy-Sepharose support (hydrophilic matrix) and then conjugated with grubbs; and in the second, the free lipase was incubated with organometallic in aqueous solution and then immobilized on epoxy-Sepharose. The different catalysts showed excellent conversion values in the ring-closing metathesis of diethyldiallymalonate in aqueous media at 25 • C.
El presente artículo pretende revisar la estructura de poblamiento romano en la Navarra Media, prestando especial atención a la presencia romana en la ciudad de Tafalla, analizando sus vestigios, su relación con otras poblaciones y revisando la red viaria en época romana. Junto a ello presentamos tres nuevos hallazgos epigráficos, uno en el término municipal de Tafalla, otro en Pueyo y el tercero en Olite. Finalmente se integra a Tafalla dentro del antiguo poblamiento vascón, proponiendo, de acuerdo con las fuentes, la identificación antigua de esta ciudad.
El presente artículo pretende revisar la estructura del poblamiento romano en la Navarra Media, prestando especial atención a la presencia romana en la ciudad de Tafalla, analizando sus vestigios, su relación con otras poblaciones y revisando la red viaria. Junto a ello, presentamos tres nuevos hallazgos epigráficos, uno en el término municipal de Tafalla, otro en Pueyo y el tercero en Olite. Finalmente se integra a Tafalla dentro del antiguo poblamiento vascón, proponiendo, de acuerdo con otras fuentes literarias, arqueológicas y epigráficas, una identificación para esta ciudad: la antigua Curnonion.
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