Search results for "nucleobase"

Excitation of Nucleobases from a Computational Perspective I: Reaction Paths

2013

The main intrinsic photochemical events in nucleobases can be described on theoretical grounds within the realm of non-adiabatic computational photochemistry. From a static standpoint, the photochemical reaction path approach (PRPA), through the computation of the respective minimum energy path (MEP), can be regarded as the most suitable strategy in order to explore the electronically excited isolated nucleobases. Unfortunately, the PRPA does not appear widely in the studies reported in the last decade. The main ultrafast decay observed experimentally for the gas-phase excited nucleobases is related to the computed barrierless MEPs from the bright excited state connecting the initial Franck…

Synthesis of 5‐Fluorocytosine Using 2‐Cyano‐2‐fluoroethenolate as a Key Intermediate

2019

Relaxation Mechanisms of 5-Azacytosine.

2015

The photophysics and deactivation pathways of the noncanonical 5-azacytosine nucleobase were studied using the CASPT2//CASSCF protocol. One of the most significant differences with respect to the parent molecule cytosine is the presence of a dark (1)(nNπ*) excited state placed energetically below the bright excited state (1)(ππ*) at the Franck-Condon region. The main photoresponse of the system is a presumably efficient radiationless decay back to the original ground state, mediated by two accessible conical intersections involving a population transfer from the (1)(ππ*) and the (1)(nNπ*) states to the ground state. Therefore, a minor contribution of the triplet states in the photophysics o…

Asymmetric and Symmetric Dicopper(II) Paddle-Wheel Units with Modified Nucleobases

2015

New copper(II) paddle-wheel complexes with different modified nucleobases and simple molecules in the axial positions have been prepared by direct reactions between copper(II) salts and the corresponding uracil- or thymine-1-acetic acids under inert atmosphere to produce the two homoleptic complexes, [Cu2(μ-OOCCH2-T)4(G)2] and [Cu2(μ-OOCCH2-U)4(G)2], and the heteroleptic one [Cu2(μ-OOCCH2-T)2(μ-OOCCH2-U)2(G)2] (where OOCCH2-T = thymine-1-acetate, OOCCH2-U = uracil-1-acetate, and G = dimethylformamide, water, dimethylacetamide, or dimethyl sulfoxide). Interestingly, the crystal structures of this family of closely related molecules present significant differences in their supramolecular arra…

Spectroscopic and electrochemical study of interactions between DNA and different salts of 1,4-dihydropyridine AV-153

2020

1,4-dihydropyridines (1,4-DHP) possess important biochemical and pharmacological properties, including antimutagenic and DNA-binding activity. The latter activity was first described for water-soluble 1,4-DHP with carboxylic group in position 4, the sodium salt of the 1,4-DHP derivative AV-153 among others. Some data show the modification of physicochemical properties and biological activities of organic compounds by metal ions that form the salts. We demonstrated the different affinity to DNA and DNA-protecting capacity of AV-153 salts, depending on the salt-forming ion (Na, K, Li, Rb, Ca, Mg). This study aimed to use different approaches to collate data on the DNA-binding mode of AV-153-N…

Studies on Adduct Formation of (+)-Anti-Benzo[a]pyrene 7,8-Dihydrodiol 9,10-Epoxide with the oligonucleotides 5′-d(CCTATCGTTATCC) and 5′-d(CCTATm5CGT…

1999

Abstract Adduct formation of (+)-anti-benzo[a]pyrene 7,8-dihydrodiol 9,10-epoxide [BPDE] and 5′-d(CCTATCGTTATCC) or 5′-d(CCTATm5CGTTATCC) (G = binding target) has been studied. The extent of trans-BPDE-N2-dG adduct formation was higher in the oligonucleotide with 5′-d(m5CG) sequence context in both single- and double stranded form compared to the non-methylated analogue. The stimulating effect of m5dC on adduct formation has previously been demonstrated in other experimental systems. The increase in yield could possibly be rationalized in terms of prestacking of the pyrenyl ring with the nucleobases prior to the nucleophilic addition. In the present study, both UV absorption and induced cir…

Bis(6-thioxo-1,6-dihydropurinium) tetrachlorozincate(II).

2006

The title salt, (C(5)H(5)N(4)S)(2)[ZnCl(4)], consists of two 6-thioxo-1,6-dihydropurinium (6mpH(2)(+)) cations (A and B) and a tetrachlorozincate anion, which are held together by N-H...Cl and C-H...Cl interactions. There is an anion-pi interaction between one Cl atom of the [ZnCl(4)](-) anion and the pyrimidine ring of the 6mpH(2)(+)(B) cation. Intermolecular pi-pi stacking interactions allow 6mpH(2)(+)(A) cations to form antiparallel pairs. One interesting structural feature is the double N-H...N intermolecular hydrogen bonds between two 6mpH(2)(+)(A) cations. This kind of interaction, mimicking that of natural nucleobases, can be very valuable in designing new therapeutic purine derivati…

Ab initio determination of the ionization potentials of DNA and RNA nucleobases

2006

Quantum chemical high level ab initio coupled-cluster and multiconfigurational perturbation methods have been used to compute vertical and adiabatic ionization potentials of the five canonical DNA and RNA nucleobases: uracil, thymine, cytosine, adenine, and guanine. Several states of their cations have been also calculated. The present results represent a systematic compendium of these magnitudes, establishing theoretical reference values at a level not reported before, calibrating computational strategies, and guiding the assignment of the features in the experimental photoelectron spectra. Daniel.Roca@uv.es Mercedes.Rubio@uv.es Manuela.Merchan@uv.es Luis.Serrano@uv.es

Experimental and theoretical studies on thymine photodimerization mediated by oxidatively generated DNA lesions and epigenetic intermediates.

2020

[EN] Interaction of nucleic acids with light is a scientific question of paramount relevance not only in the understanding of life functioning and evolution, but also in the insurgence of diseases such as malignant skin cancer and in the development of biomarkers and novel light-assisted therapeutic tools. This work shows that the UVA portion of sunlight, not absorbed by canonical DNA nucleobases, can be absorbed by 5-formyluracil (ForU) and 5-formylcytosine (ForC), two ubiquitous oxidatively generated lesions and epigenetic intermediates present in living beings in natural conditions. We measure the strong propensity of these molecules to populate triplet excited states able to transfer th…

DNA damage photo-induced by chloroharmine isomers: hydrolysis versus oxidation of nucleobases

2018

Photodynamic therapy (PDT) is an emerging clinical treatment currently being used against a wide range of both cancerous and noncancerous diseases. The search for new active photosensitizers as well as the development of novel selective delivery systems are the major challenges faced in the application of PDT. We investigated herein three chloroharmine derivatives (6-, 8- and 6,8-dichloroharmines) with quite promising intrinsic photochemical tunable properties and their ability to photoinduce DNA damage in order to elucidate the underlying photochemical mechanisms. Data revealed that the three compounds are quite efficient photosensitizers. The overall extent of photo-oxidative DNA damage i…