Biochemical and Structural Characterization of a Schiff Base in the Radical-Mediated Biosynthesis of 4-Demethylwyosine by TYW1

TYW1 is a radical S-adenosyl-l-methionine (SAM) enzyme that catalyzes the condensation of pyruvate and N-methylguanosine to form the posttranscriptional modification, 4-demethylwyosine, in situ on transfer RNA (tRNA). Two mechanisms have been proposed for this transformation, with one of the possible mechanisms invoking a Schiff base intermediate formed between a conserved lysine residue and pyruvate. Utilizing a combination of mass spectrometry and X-ray crystallography, we have obtained evidence to support the formation of a Schiff base lysine adduct in TYW1. When 13 C labeled pyruvate is used, the mass shift of the adduct matches that of the labeled pyruvate, indicating that pyruvate is the source of the adduct. Furthermore, a crystal structure of TYW1 provides visualization of the Schiff base lysine-pyruvate adduct, which is positioned directly adjacent to the auxiliary [4Fe-4S] cluster. The adduct coordinates the unique iron of the auxiliary cluster through the lysine nitrogen and a carboxylate oxygen, reminiscent of how the radical SAM [4Fe-4S] cluster is coordinated by SAM. The structure provides insight into the binding site for tRNA and further suggests how radical SAM chemistry can be combined with Schiff base chemistry for RNA modification.National Science Foundation (U.S.) (Grant 1122374

Transport Properties of Highly Aligned Polymer Light-Emitting-Diodes

We investigate hole transport in polymer light-emitting-diodes in which the emissive layer is made of liquid-crystalline polymer chains aligned perpendicular to the direction of transport. Calculations of the current as a function of time via a random-walk model show excellent qualitative agreement with experiments conducted on electroluminescent polyfluorene demonstrating non-dispersive hole transport. The current exhibits a constant plateau as the charge carriers move with a time-independent drift velocity, followed by a long tail when they reach the collecting electrode. Variation of the parameters within the model allows the investigation of the transition from non-dispersive to dispersive transport in highly aligned polymers. It turns out that large inter-chain hopping is required for non-dispersive hole transport and that structural disorder obstructs the propagation of holes through the polymer film.Comment: 4 pages, 5 figure

Including a Cold Pool Representation in a Convection Parameterization and Simulating Its Impacts on the Spatial and Temporal Variability of the Precipitation in the NASA GEOS GCM

We developed and implemented a simple representation of a cold pool in the Grell-Freitas (GF) convection parameterization. The cold pool parameterization is based on the observation that convective-scale downdrafts produce a local deficit of the moist static energy (MSE). This information is advected and becoming downwind available to trigger and intensify new convection. The cold pool is dissipated by a simple exponential decay using a lifetime of a few hours, or by interacting with the underneath surface by exchanging latent and sensible heat fluxes. Preliminary results show some improvement of the simulation of the diurnal cycle of the precipitation over the land, mainly during the nighttime

Technology Platform for Sampling Water with Electrolyte-Gated Organic Transistors Sensitised with Langmuiur-Deposited Calixarene Surface Layers.

We demonstrate a technology platform that enables the development of new, surface-sensitised organic transistor sensors. We show that an organic semiconductor can still be gated by an electric double layer within the electrochemical window of water after the deposition of up to four Langmuir- Schäfer calixarene layers onto its surface. Since many calixarenes are known to selectively bind waterborne cations, this facilitates sensitising a conventional organic semiconductor with a physically deposited layer for specific cation recognition. When at least two Langmuir-Schäfer layers are deposited, these also block the electrochemical doping of the organic semiconductor, which otherwise competes with the field effect in water-gated organic transistors. Carrier mobility is reduced by the application of calixarene layers, but transistor current measurement remains accessible by simple methods. We find that for the present purpose, Langmuir-Schäfer-printed surface layers perform better than those deposited by Langmuir-Blodgett deposition