Pump-probe differencing technique for cavity-enhanced, noise-canceling saturation laser spectroscopy

We present an experimental technique that permits mechanical-noise-free, cavity-enhanced frequency measurements of an atomic transition and its hyperfine structure. We employ the 532-nm frequency-doubled output from a Nd:YAG laser and an iodine vapor cell. The cell is placed in a folded ring cavity (FRC) with counterpropagating pump and probe beams. The FRC is locked with the Pound-Drever-Hall technique. Mechanical noise is rejected by differencing the pump and probe signals. In addition, this differenced error signal provides a sensitive measure of differential nonlinearity within the FRC.     

<Emphasis Type="Italic">α</Emphasis>-Synuclein: Stable compact and extended monomeric structures and pH dependence of dimer formation

The protein alpha-synuclein, implicated in Parkinson's disease, was studied by combining nano-electrospray ionization (N-ESI) mass spectrometry and ion mobility. It was found that both the charge-state distribution in the mass spectra and the average protein shape deduced from ion mobility data, depend on the pH of the spray solution. Negative-ion N-ESI of pH 7 solutions yielded a broad charge-state distribution from -6 to -16, centered at -11, and ion mobility data consistent with extended protein structures. Data obtained for pH 2.5 solutions, on the other hand, showed a narrow charge-state distribution from -6 to -11, centered at -8, and ion mobilities in agreement with compact alpha-synuclein structures. The data indicated that there are two distinct families of structures: one consisting of relatively compact proteins with eight or less negative charges and one consisting of relatively extended structures with nine or more charges. The average cross section of a-synuclein at pH 2.5 is 33% smaller than for the extended protein sprayed from pH 7 solution. Significant dimer formation was observed when sprayed from pH 7 solution but no dimers were observed from the low pH solution. A plausible mechanism for aggregate formation in solution is proposed.     

Proton transfer versus redox modulation in thiourea-phenanthrenequinone molecular and polymeric complexes

Phenanthrenequinone undergoes highly efficient proton transfer processes in the presence of a thiourea-functionalised polystyrene copolymer whereas interactions with a similar benzyl-thiourea monomer show strong redox modulation of the quinone without proton transfer.     

First search for the flavor changing neutral current decay D0-->gammagamma

Using 13.8 fb(-1) of data collected at or just below the Upsilon(4S) with the CLEO detector, we report the result of a search for the flavor changing neutral current process D0-->gammagamma. We observe no significant signal for this decay mode and determine 90% confidence level upper limits on the branching fractions B(D0-->gammagamma)/B(D0-->pi(0)pi(0))<0.033 and B(D0-->gammagamma)<2.9 x 10(-5).     

Thermally reversible formation of microspheres through non-covalent polymer cross-linking

Bis-thymine units were used to noncovalently cross-link a complementary diamidopyridine-functionalized copolymer. Upon combination in noncompetitive solvents, discrete micron-scale spherical aggregates were formed arising from specific three-point polymer-cross-linker hydrogen bonding interactions. The diameter of these microspheres could be controlled through spacer structure. The cross-linking process was fully thermally reversible, with complete dissolution observed at 50 degrees C and reformation of the aggregates upon return to ambient temperature. This process could be repeated multiply, with lower particle dispersity observed arising from the annealing process.     

Model systems for flavoenzyme activity: relationships between cofactor structure, binding and redox properties

A series of flavins were synthesized bearing electron-withdrawing and -donating substituents. The electrochemical properties of these flavins in a nonpolar solvent were determined. The recognition of these flavins by a diamidopyridine (DAP) receptor and the effect this receptor has on flavin redox potential was also quantified. It was found that the DAP-flavin binding affinity and the reduction potentials (E(1/2)) for both the DAP-bound and unbound flavins correlated well with functions derived from linear free energy relationships (LFERs). These results provide insight and predictive capability for the interplay of electronics and redox state-specific interactions for both abiotic and enzymatic systems.     

Redox modulation of benzene triimides and diimides via noncovalent interactions

[reaction: see text] Mellitic triimides undergo three sequential one-electron reduction processes whose potentials are significantly lowered in the presence of alkyl thioureas. The two sequential reductions of benzene diimides are similarly stabilized. Calculation of the relative free energy change between the different electronic states of the imide acceptors and their corresponding alkyl thiourea complexes indicates dramatic increases in hydrogen bond strength with increasing acceptor charge density.     

Evaluation of the two-dimensional reversed-phase-reversed-phase separations of low-molecular mass polystyrenes

The resolving power of four reversed-phase-reversed-phase two-dimensional (2D) chromatographic systems was evaluated using information theory (IT) and a geometric approach to factor analysis. The first separation dimension employed a C18 column, while the second separation dimension employed a carbon clad zirconia column. Mobile phases in each dimension were either methanol or acetonitrile. The sample matrix that was employed in this study contained a mixture of 58 components, comprised of stereoisomers and structural isomers of a systematic variation in molecular weight. Each of the components were oligostyrenes, with between two and five configurational repeating units having either n-butyl, sec-butyl or tert-butyl end groups. In the two-dimensional systems employed in this study, between 46 and 49 of the 58 components could be separated, depending on the mobile phase combinations--with apparent resolution that could not possibly be achieved in a single one-dimensional separation. The results from this study indicate that in order to fully evaluate the resolving power of a 2D system multiple methods of analysis that evaluate the separation potential are most appropriate. This becomes increasingly important when the sample contains components that are very closely related and the retention of solutes displays a high degree of solute crowding.     

The Ergodic Theory of Traffic Jams

We introduce and analyze a simple probabilistic cellular automaton which emulates the flow of cars along a highway. Our Traffic CA captures the essential features of several more complicated algorithms, studied numerically by K. Nagel and others over the past decade as prototypes for the emergence of traffic jams. By simplifying the dynamics, we are able to identify and precisely formulate the self-organized critical evolution of our system. We focus here on the Cruise Control case, in which well-spaced cars move deterministically at maximal speed, and we obtain rigorous results for several special cases. Then we introduce a symmetry assumption that leads to a two-parameter model, described in terms of acceleration () and braking () probabilities. Based on the results of simulations, we map out the (, ) phase diagram, identifying three qualitatively distinct varieties of traffic which arise, and we derive rigorous bounds to establish the existence of a phase transition from free flow to jams. Many other results and conjectures are presented. From a mathematical perspective, Traffic CA provides local, particle-conserving, one-dimensional dynamics which cluster, and converge to a mixture of two distinct equilibria.