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Ultrafast Excited-State Dynamics of Hydrogen-Bonded Cytosine Microsolvated Clusters with Protic and Aprotic Polar Solvents
摘要： Microsolvation effects on the ultrafast excited-state deactivation dynamics of cytosine (Cy) were studied in hydrogen-bonded Cy clusters with protic and aprotic solvents using mass-resolved femtosecond pump-probe ionization spectroscopy. Two protic solvents, water (H2O) and methanol (MeOH), and one aprotic solvent, tetrahydrofuran (THF), were investigated, and transients of Cy·(H2O)1-6, Cy·(MeOH)1-3, and Cy·THF microsolvated clusters produced in supersonic expansions were measured. With the aid of electronic structure calculations, we assigned the observed dynamics to the low-energy isomers of various Cy clusters and discussed the microsolvation effect on the excited-state deactivation dynamics. With the protic solvents only the microsolvated clusters of Cy keto tautomer were observed. The observed decay time constants of Cy·(H2O)n are 0.5 ps for n=1 and ~0.2–0.25 ps for n=2–6. For Cy·(MeOH)n clusters, the decay time constant for n=1 cluster is similar to that of the Cy monohydrate, but for n=2 and 3 the decays are about a factor of two slower than the corresponding microhydrates. With the aprotic solvent, THF, hydrogen-bonded complexes of both keto and enol tautomers are present in the beam. The keto-Cy·THF shows a similar decay as the keto-Cy monomer, whereas the enol-Cy·THF exhibits a two-fold slower decay than the enol-Cy monomer, suggesting an increase in the barrier to excited-state deactivation upon binding of one THF molecule to the enol form of Cy.
关键词： Cytosine,Excited-state deactivation,Hydrogen-bonded clusters,Microsolvation,Ultrafast dynamics
更新于2025-09-23 15:21:01
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Locating Cytosine Conical Intersections by Laser Experiments and <i>Ab Initio</i> Calculations
摘要： The decay mechanism of S1 excited cytosine (Cyt) and the effect of substitution are studied combining jet-cooled spectroscopy (nanosecond resonant two-photon ionization (R2PI) and picosecond lifetime measurements) with CASPT2//CASSCF computations for eight derivatives. For Cyt and five derivatives substituted at N1, C5, and C6, rapid internal conversion sets in at 250?1200 cm?1 above the 000 bands. The break-off in the spectra correlates with the calculated barriers toward the "C5?C6 twist" conical intersection, which unambiguously establishes the decay mechanism at low S1 state vibrational energies. The barriers increase with substituents that stabilize the charge shifts at C4, C5, and C6 following (1ππ*) excitation. The R2PI spectra of the clamped derivatives 5,6-trimethyleneCyt (TMCyt) and 1-methyl-TMCyt (1M-TMCyt), which decay along an N3 out-of-plane coordinate, extend up to +3500 and +4500 cm?1.
关键词： CASPT2//CASSCF computations,jet-cooled spectroscopy,internal conversion,substitution effect,R2PI spectra,decay mechanism,cytosine,conical intersection
更新于2025-09-23 15:19:57
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A host dTMP-bound structure of T4 phage dCMP hydroxymethylase mutant using an X-ray free electron laser
摘要： The hydroxymethylation of cytosine bases plays a vital role in the phage DNA protection system inside the host Escherichia coli. This modification is known to be catalyzed by the dCMP hydroxymethylase from bacteriophage T4 (T4dCH); structural information on the complexes with the substrate, dCMP and the co-factor, tetrahydrofolate is currently available. However, the detailed mechanism has not been understood clearly owing to a lack of structure in the complex with a reaction intermediate. We have applied the X-ray free electron laser (XFEL) technique to determine a high-resolution structure of a T4dCH D179N active site mutant. The XFEL structure was determined at room temperature and exhibited several unique features in comparison with previously determined structures. Unexpectedly, we observed a bulky electron density at the active site of the mutant that originated from the physiological host (i.e., E. coli). Mass-spectrometric analysis and a cautious interpretation of an electron density map indicated that it was a dTMP molecule. The bound dTMP mimicked the methylene intermediate from dCMP to 5′-hydroxymethy-dCMP, and a critical water molecule for the final hydroxylation was convincingly identified. Therefore, this study provides information that contributes to the understanding of hydroxymethylation.
关键词： hydroxymethylation,XFEL,dCMP hydroxymethylase,X-ray free electron laser,T4dCH,hydroxylation,cytosine bases,phage DNA protection,dTMP,Escherichia coli,bacteriophage T4,methylene intermediate
更新于2025-09-12 10:27:22