A novel laser-based apparatus is presented utilizing high harmonic radiation for visible pump–EUV probe experiments on ultrafast processes. True femtosecond temporal resolution is achieved by a monochromator making use of dedicated narrowband multilayer mirrors rather than gratings for selection of single harmonic orders in the photon energy range between 66 and 73 eV. First applications of this new light source for electron spectroscopy on gas phase helium and xenon demonstrate the selection of a single high harmonic order with the intensity ratio between the selected and its adjacent harmonic not exceeding 10:1. A pump–probe study of hot electron production on a solid Pt(110) surface yields a cross-correlation corresponding to a temporal system resolution of 100 fs.

No abstract

An irreversible electronic energy trap has been formed in calf thymus DNA by methylating about 75% of its G bases at position N-7. This has allowed us to measure for the first time the efficiency of transfer of energy along the helix of a double-stranded nucleic acid at room temperature. It is found that about one out of every three photons absorbed by the other bases is trapped. We have also simulated the data with a stochastic model that uses the dipole-dipole interaction to calculate the efficiency of transfer. In order to approximate the experimental results, the model requires that: (i) the fluorescence quantum yield of T, C, and G in DNA be about 2 x 10(-3), which is about two orders of magnitude larger than the value of the fluorescence quantum yield reported for DNA; and (ii) the fluorescence quantum yield of A in DNA be negligibly small. Requirement (i) is consistent with energy transfer taking place before a very efficient fluorescence quenching process sets in, which could be formation of excited-state complexes (excimers) that do not fluoresce appreciably. Requirement (ii) implies a very short fluorescence lifetime for A, which is consistent with the reported absence of a significant number of photoproducts formed by A in DNA. The simulations find that, on the average, the excitation energy takes about 1.2 steps to reach the trap; that is to say, bases that are nearest and next nearest neighbors of the trap are, in effect, the only energy donors. Both intra- as well as interstrand energy transfer (the latter only for the C-trap base pair) make significant contributions. The value of the efficiency for pairwise base-base intrastrand transfer is about 60%, whereas those for base-trap intra- and interstand transfer are 90% and 80%, respectively. The corresponding values for the rate constant of transfer are 2 x 10(11), 1 x 10(12), and 4 x 10(11) s-1. Transfer is inefficient when A is the donor or the acceptor. In addition to the dipole-dipole term, the only other significant term in the expansion of the interaction potential is the dipole-quadrupole term which, however, makes only a small contribution to the overall transfer efficiency. The electron exchange interaction appears to be much less efficient than the coulombic interaction.

We have made room-temperature measurements of transfer of electronic energy in calf thymus DNA in which 75% of the guanine residues are methylated at position N-7. The methylated residues absorb light at much longer wavelengths than the nonmethylated residues and, as a result, constitute an irreversible energy trap. For excitation at 270 nm the efficiency of intrastrand transfer is found to be 0.31. We note that this is the first measurement of the efficiency of energy transfer along the double helix of a nucleic acid.In addition, the data have been simulated by using a stochastic model in terms of Förster's theory for dipole-dipole transfer. The adequacy of the latter is discussed.Preliminary measurements of the dependence of the fluorescence spectrum and of the fluorescence anisotropy of the alternating polynucleotide poly(dA-dT).poly(dA-dT) on the excitation wavelength and temperature are interpreted in terms of emission from molecular complexes formed between A and T residues.

No abstract