Search results for "thymine"

A surface hopping algorithm for nonadiabatic minimum energy path calculations

2015

The article introduces a robust algorithm for the computation of minimum energy paths transiting along regions of near-to or degeneracy of adiabatic states. The method facilitates studies of excited state reactivity involving weakly avoided crossings and conical intersections. Based on the analysis of the change in the multiconfigurational wave function the algorithm takes the decision whether the optimization should continue following the same electronic state or switch to a different state. This algorithm helps to overcome convergence difficulties near degeneracies. The implementation in the MOLCAS quantum chemistry package is discussed. To demonstrate the utility of the proposed procedur…

On the Deactivation Mechanisms of Adenine–Thymine Base Pair

2012

In this contribution, the multiconfigurational second-order perturbation theory method based on a complete active space reference wave function (CASSCF/CASPT2) is applied to study all possible single and double proton/hydrogen transfers between the nucleobases in the adenine-thymine (AT) base pair, analyzing the role of excited states with different nature [localized (LE) and charge transfer (CT)], and considering concerted as well as step-wise mechanisms. According to the findings, once the lowest excited states, localized in adenine, are populated during UV irradiation of the Watson-Crick base pair, the proton transfer in the N-O bridge does not require high energy in order to populate a …

Complete-active-space second-order perturbation theory (CASPT2//CASSCF) study of the dissociative electron attachment in canonical DNA nucleobases ca…

2015

Low-energy (0-3 eV) ballistic electrons originated during the irradiation of biological material can interact with DNA/RNA nucleobases yielding transient-anion species which undergo decompositions. Since the discovery that these reactions can eventually lead to strand breaking of the DNA chains, great efforts have been dedicated to their study. The main fragmentation at the 0-3 eV energy range is the ejection of a hydrogen atom from the specific nitrogen positions. In the present study, the methodological approach introduced in a previous work on uracil [I. González-Ramírez et al., J. Chem. Theory Comput. 8, 2769-2776 (2012)] is employed to study the DNA canonical nucleobases fragmentations…

Determination of the lowest-energy oxidation site in nucleotides: 2'-deoxythymidine 5'-monophosphate anion.

2006

High level ab initio computations anticipate nucleobases as the most favorable sites for oxidation in nucleotides. At the CASPT2 level, the lowest ionization channel for the 2'-deoxythymidine 5'-monophosphate anion is related to a pi-orbital of the thymine base. The present findings lead to revision of the recent assignments of the photodetachment photoelectron spectra of mononucleotide anions in the gas phase and support the classical view of the nucleobase being the main actor in the oxidation process of both nucleosides and nucleotides.

EFFECTS OF SENSITIZED AND UNSENSITIZED LONGWAVE U.V.-IRRADIATION ON THE SOLUTION PROPERTIES OF DNA

1971

— Two types of photoreactions occur in DNA irradiated in aqueous systems with longwave u.v.-light (Λ > 295 nm), namely, (a) thymine dimerization, and (b) single- and double-strand breakage of the sugar phosphate backbone; these two reactions are unrelated. The presence of acetophenone as a photosensitizer caused an increase in dimerization by a factor of 16, and an increase in single-strand breaks by a factor of 4. The number of thymine dimers per single-strand break is about 100 in the sensitized and 25 in the unsensitized reaction. The alteration of the radius of gyration of DNA molecules is that expected by the degradation observed. At the same time the change in hyperchromicity is very …

The determination of the DNA base composition in 19 species of adriatic sponges with high-pressure liquid cation-exchange chromatography.

1976

Abstract The (adenine + thymine)/(guanine + cytosine) base ratios of 19 species of adriatic sponges have been determined by high-pressure liquid cation-exchange chromatography. The base ratios vary from 1.49 (Mycale massa) to 0.63 (Hippospongia communis) according to an (A+T) content of 59.7 and 38.6 mol%, respectively. The DNAs of sponges of the order Keratosa showed marked differences in their (A +T) contents (39.5 to 58.8 mol%) whereas those of Tetractinellida and Halichondrina were nearly identical (39.3 to 40.8 and 49.5 to 49.8 mol%, respectively). The 5-methylcytosine (5MC) content was determined in 8 sponge DNAs by a semiquantitative method. The values differed from 0.8 to 2.2 mol% o…

Thymine content of sea water as a measure of biosynthetic potential

1977

A hydrolysis procedure along with a high-pressure liquid chromatographic procedure is given enabling simple and reliable thymine determinations in the nanogram range in different fractions of sea-water samples taken from three different locations in the Northern Adriatic Sea. The levels corresponded to 1–3 μg DNA per liter. From total polyanionic thymine, which had been precipitated as the cetyltrimethylammonium salt, the highest percentage was linked to the particulate fraction, with a definite subsurface minimum at 10 to 15 m. There was a corresponding maximum of a high molecular “non-particulate” thymine-containing fraction at the corresponding depth. From the bottom at 30 m upwards to a…

Micro-determination of DNA in biological materials by gas-chromatographic and isotope dilution analysis of thymine content

1970

Bleomycin, an Antibiotic That Removes Thymine from Double-Stranded DNA

1977

Publisher Summary This chapter reviews that bleomycins are members of a new class of DNA-modifying agents, the quasi-enzymes. In in vitro systems, bleomycin first removes thymines from native DNA by hydrolysis of the N-glycosidic bonds without modifying the deoxyribose moiety. In a second step, single-strand scissions occur at the sites of the nonglycosidic deoxyribose moieties, resulting in the formation of 3'-OH and 5'-P termini. It is suggested that bleomycin is bound to DNA by interaction of the positively charged terminal amine moiety with the negatively charged phosphate group in DNA; intercalation seems to be involved in binding. Bleomycin is inactivated by copper and zinc ions, prob…

Singlet oxygen generation in PUVA therapy studied using electronic structure calculations

2009

Abstract The ability of furocoumarins to participate in the PUVA (Psoralen + UV-A) therapy against skin disorders and some types of cancer, is analyzed on quantum chemical grounds. The efficiency of the process relies on its capability to populate its lowest triplet excited state, and then either form adducts with thymine which interfere DNA replication or transfer its energy, generating singlet molecular oxygen damaging the cell membrane in photoactivated tissues. By determining the spin–orbit couplings, shown to be the key property, in the intersystem crossing yielding the triplet state of the furocoumarin, the electronic couplings in the triplet–triplet energy transfer process producing …