RESUMO
Gas-phase near-edge X-ray-absorption fine structure (NEXAFS) action spectroscopy around the oxygen K-edge and mass spectrometry were employed to probe isolated substance P (SP) molecular ions, both bare and progressively solvated with 4 and 11 water molecules. Detailed mass spectra of bare and hydrated precursors are presented for the resonant photon energy of 532 eV that corresponds to O1s âπ(amide)* core excitation, triggering resonant Auger decay and fragmentation from the ionized radical molecular system. The fragmentation pattern of doubly protonated SP hydrated with 4 water molecules clearly shows a series of abundant doubly charged backbone fragments, as well as triply charged precursor with small neutral losses, all preserving full water cluster. This is drastically different from the collisional induced dissociation of the hydrated peptide where the water loss is a dominant relaxation process. Moreover, the action NEXAFS obtained from several resolved small backbone fragments revealed increased fragmentation of hydrated SP relative to the bare one, due to a resonant O1s excitation of the attached water molecules. Such unexpected result inspires further experimental developments to investigate possible nonlocal energy transfer from the solvent to the biomolecules within the first solvation shell. The experiment is supported by molecular dynamics and DFT calculations to estimate the intensity of the resonant X-ray absorption of bare and hydrated SP around peptide and water O1s excitation region.
Assuntos
Oxigênio/química , Peptídeos/química , Transferência de Energia , Fótons , Solubilidade , Espectroscopia por Absorção de Raios XRESUMO
2-Fluoroadenine ((2F) A) is a therapeutic agent, which is suggested for application in cancer radiotherapy. The molecular mechanism of DNA radiation damage can be ascribed to a significant extent to the action of low-energy (<20â eV) electrons (LEEs), which damage DNA by dissociative electron attachment. LEE induced reactions in (2F) A are characterized both isolated in the gas phase and in the condensed phase when it is incorporated into DNA. Information about negative ion resonances and anion-mediated fragmentation reactions is combined with an absolute quantification of DNA strand breaks in (2F) A-containing oligonucleotides upon irradiation with LEEs. The incorporation of (2F) A into DNA results in an enhanced strand breakage. The strand-break cross sections are clearly energy dependent, whereas the strand-break enhancements by (2F) A at 5.5, 10, and 15â eV are very similar. Thus, (2F) A can be considered an effective radiosensitizer operative at a wide range of electron energies.
Assuntos
Adenina/análogos & derivados , DNA/química , Elétrons , Teoria Quântica , Adenina/químicaRESUMO
Understanding the competing processes that govern far ultraviolet photodissociation (FUV-PD) of biopolymers such as proteins is a challenge. Here, we report a combined experimental and theoretical investigation of FUV-PD of protonated leucine-enkephalin pentapeptide ([YGGFL + H]+) in the gas-phase. Time-dependent density functional theory (TD-DFT) calculations in combination with experiments and previous results for amino acids and shorter peptides help in rationalizing the evolution of the excited states. The results confirm that fragmentation of [YGGFL + H]+ results mainly from vibrationally excited species in the ground electronic state, populated after internal conversion. We also propose fragmentation mechanisms for specific photo-fragments such as tyrosine side chain loss (with an extra hydrogen) or hydrogen loss. In general, we observe the same mechanisms as for smaller peptides or protonated Tyr and Phe, that are not quenched by the presence of other amino acids. Nevertheless, we also found some differences, as for H loss, in part due to the fact that the charge is solvated by the peptide chain and not only by the COOH terminal group.
RESUMO
The photodissociation of gaseous protonated adenosine 5'-monophosphate (AMP) and the same system hydrated with one water molecule has been investigated in the 4 to 13 eV photon energy range by coupling a linear quadrupole ion trap with a synchrotron radiation beamline. The dissociation of the bare AMP cation upon absorption of a single ultraviolet (UV) photon below the ionization energy (IE) almost exclusively produces the protonated adenine base, with a measured photodissociation yield showing spectroscopic features with dominant absorption bands located at 4.75 and 6.5 eV, found in agreement with TD-DFT calculations. Nevertheless, the addition of a single water molecule to the system modifies the dissociation energy dependence and strongly suppresses the cleavage of the glycosidic CN bond below the IE. Both the experimental and theoretical results suggest that a single solvent molecule can intrinsically influence the structure and physicochemical properties of the AMP cation, including its UV induced dissociation pattern, beyond the simple water evaporation.