RESUMO
2,6-Diaminopurine (2,6-dAP) is an alternative nucleobase that potentially played a role in prebiotic chemistry. We studied its excited state dynamics in the gas phase by REMPI, IR-UV hole burning, and ps pump-probe spectroscopy and performed quantum chemical calculations at the SCS-ADC(2) level of theory to interpret the experimental results. We found the 9H tautomer to have a small barrier to ultrafast relaxation via puckering of its 6-membered ring. The 7H tautomer has a larger barrier to reach a conical intersection and also has a sizable triplet yield. These results are discussed relative to other purines, for which 9H tautomerization appears to be more photostable than 7H and homosubstituted purines appear to be less photostable than heterosubstituted or singly substituted purines.
RESUMO
Isoguanine is an alternative nucleobase that has been proposed as a component of expanded genetic codes. It has also been considered as a molecule with potential relevance to primordial informational polymers. Here, we scrutinize the photodynamics of isoguanine, because photostability has been proposed as a critical criterion for the prebiotic selection of biomolecular building blocks on an early Earth. We discuss resonance-enhanced multiphoton ionization, IR-UV double resonance spectroscopy and pump-probe measurements performed for this molecule to track the excited-state behaviour of its different tautomeric forms in the gas phase. These experiments, when confronted with highly accurate quantum chemical calculations and nonadiabatic dynamics simulations provide a complete mechanistic picture of the tautomer-specific photodynamics of isoguanine. Our results indicate that UV-excited enol tautomers of isoguanine are relatively short lived and therefore photostable. In contrast, the biologically more relevant keto forms are trapped in dark nπ* states which are sufficiently long lived to participate in destructive photochemistry. The resulting lower photostability compared to canonical nucleobases may have been one of the reasons why isoguanine was not incorporated into DNA and RNA.
Assuntos
DNA/química , Guanina/química , Modelos Moleculares , Cinética , Oxirredução , Processos Fotoquímicos , Teoria Quântica , TermodinâmicaRESUMO
Peptidomimetics that can coordinate transition metals have a variety of potential applications as catalysts, sensors, or materials. A new modular peptidomimetic scaffold, the "azole peptoid", is introduced here. We report methods for the solid-phase synthesis of eleven examples of trimeric N-substituted oligoamides that include oxazole- or thiazole-functionalized backbones. The products prepared comprise a diversity of functionality, including a metal-coordinating terpyridine group. The modular synthetic approach enables ready preparation of analogs for specific applications. To highlight a potential use of this new synthetic scaffold, a trimeric azole peptoid functionalized with a terpyridine residue was prepared and studied. The characteristic 2:1 ligand:metal binding of this terpyridine-functionalized azole peptoid to Zn2+ in aqueous solution was observed. These studies introduce azole peptoids as a useful class of biomimetic molecules for further study and application.
Assuntos
Azóis/química , Peptidomiméticos/síntese química , Peptoides/síntese química , Zinco/química , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Modelos Moleculares , Estrutura Molecular , Peptidomiméticos/química , Peptoides/química , Técnicas de Síntese em Fase Sólida , Água/químicaRESUMO
We present resonant two-photon ionization (R2PI) spectra of isocytosine (isoC) and pump-probe results on two of its tautomers. IsoC is one of a handful of alternative bases that have been proposed in scenarios of prebiotic chemistry. It is structurally similar to both cytosine (C) and guanine (G). We compare the excited-state dynamics with the Watson-Crick (WC) C and G tautomeric forms. These results suggest that the excited-state dynamics of WC form of G may primarily depend on the heterocyclic substructure of the pyrimidine moiety, which is chemically identical to isoC. For WC isoC we find a single excited-state decay with a rate of â¼1010 s-1, while the enol form has multiple decay rates, the fastest of which is 7 times slower than for WC isoC. The excited-state dynamics of isoC exhibits striking similarities with that of G, more so than with the photodynamics of C.