Femtosecond dynamics of DNA-mediated electron transfer

Diverse biophysical and biochemical studies have sought to understand electron transfer (ET) in DNA in part because of its importance to DNA damage and its repair. However, the dynamics and mechanisms of the elementary processes of ET in this medium are not fully understood and have been heavily debated. Two fundamental issues are the distance over which charge is transported and the time-scale on which the transport through the π-stack of the DNA base pairs may occur. With femtosecond resolution, we report direct observation in DNA of ultrafast ET, initiated by excitation of tethered ethidium (E), the intercalated electron acceptor (A); the electron donor (D) is 7-deazaguanine (Z), a modified base, placed at different, fixed distances from A. The ultrafast ET between these reactants in DNA has been observed with time constants of 5 ps and 75 ps and was found to be essentially independent of the D–A separation (10–17 Å). However, the ET efficiency does depend on the D–A distance. The 5-ps decay corresponds to direct ET observed from 7-deazaguanine but not guanine to E. From measurements of orientation anisotropies, we conclude that the slower 75-ps process requires the reorientation of E before ET, similar to E/nucleotide complexes in water. These results reveal the nature of ultrafast ET and its mechanism: in DNA, ET cannot be described as in proteins simply by a phenomenological parameter, β. Instead, the involvement of the base pairs controls the time scale and the degree of coherent transport.

Grain size composition of sediment cores from the Weddell Sea, Antarctica

Sedimentary processes in the southeastern Weddell Sea are influenced by glacial-interglacial ice-shelf dynamics and the cyclonic circulation of the Weddell Gyre, which affects all water masses down to the sea floor. Significantly increased sedimentation rates occur during glacial stages, when ice sheets advance to the shelf edge and trigger gravitational sediment transport to the deep sea. Downslope transport on the Crary Fan and off Dronning Maud and Coats Land is channelized into three huge channel systems, which originate on the eastern-, the central and the western Crary Fan. They gradually turn from a northerly direction eastward until they follow a course parallel to the continental slope. All channels show strongly asymmetric cross sections with well-developed levees on their northwestern sides, forming wedge-shaped sediment bodies. They level off very gently. Levees on the southeastern sides are small, if present at all. This characteristic morphology likely results from the process of combined turbidite-contourite deposition. Strong thermohaline currents of the Weddell Gyre entrain particles from turbidity-current suspensions, which flow down the channels, and carry them westward out of the channel where they settle on a surface gently dipping away from the channel. These sediments are intercalated with overbank deposits of high-energy and high-volume turbidity currents, which preferentially flood the left of the channels (looking downchannel) as a result of Coriolis force. In the distal setting of the easternmost channel-levee complex, where thermohaline currents are directed northeastward as a result of a recirculation of water masses from the Enderby Basin, the setting and the internal structures of a wedge-shaped sediment body indicate a contourite drift rather than a channel levee. Dating of the sediments reveals that the levees in their present form started to develop with a late Miocene cooling event, which caused an expansion of the East Antarctic Ice Sheet and an invigoration of thermohaline current activity.