Some of the most highly active organic electro-optic (EO) materials developed recently rely on the combination of an EO-active (chromophore-containing) host material (dendrimer or side-chain polymer) and an EO-active (chromophore) guest. These new binary-chromophore materials exhibit EO coefficients (r 33 ) in the range of 250 to greater than 300 pm/V (currently as high as 450 pm/V). The EO activity of these binary-chromophore materials is greater the sum of their individual components. The experimentally observed increase in the nonlinear optical response of two representative classes of EO chromophore-EO dendrimer and EO chromophore-EO polymer mixtures relative to the response of the isolated components is described quantitatively herein by a physical model that accounts for cooperativity in the guest-host interactions.

Steered molecular dynamics simulations are combined with analytic theory in order to gain insights into the properties of the P-selectin/PSGL-1 catch-slip bond at the atomistic level of detail. The simulations allow us to monitor the conformational changes in the P-selectin/PSGL-1 complex in response to an external force, while the theory provides a unified framework bridging the simulation data with experiment over 9 orders of magnitude. The theory predicts that the probability of bond dissociation by the catch mechanism is extremely low in the simulations; however, a few or even a single trajectory can be sufficient for characterization of the slip mechanism. Theoretical analysis of the simulation data shows that the bond responds to the force in a highly nonlinear way, with the bond stiffness changing considerably as a function of the force ramp rate. The Langevin description of the simulation provides spring constants of the proteins and the binding interaction and gives the friction coefficient associated with the receptor-ligand motion in water. The estimated relaxation time shows that the simple probabilistic description is accurate for the experimental regime and remains approximately valid for the high ramp rates used in simulations. The simulations establish that bond deformation occurs primarily within the P-selectin receptor region. The two interaction sites within the binding pocket dissociate sequentially, raising the possibility of observing these independent rupture events in experiment. The stronger interaction that determines the overall properties of the bond dissociates first, indicating that the experimental data indeed capture the main rupture event and not the secondary weaker site rupture. The main rupture event involves the interaction between the calcium ion of the receptor and the ligand residue FUC-623. It is followed by new interactions, supporting the sliding-rebinding behavior observed in the earlier simulation [ Lou, J. Zhu, C. Biophys. J. 2007 , 92 , 1471 - 1485 ]. The weaker binding site shows fewer interaction features, suggesting that the sliding-rebinding behavior may be determined by the unique properties of the calcium site. The agreement between simulation and experiment provided by the two-pathway and deformation models, each containing only four parameters, indicates that the essential physics of the catch-slip bond should be relatively simple and robust over a wide range of pulling regimes.

The results of our earlier work [C. Brooksby, O. V. Prezhdo, and P. J. Reid, J. Chem. Phys. 119, 9111 (2003)] rationalizing the surprisingly weak solvent dependence of the dynamics following photoexcitation of chlorine dioxide in water, chloroform, and cyclohexane are thoroughly tested. Comparisons are made between equilibrium and nonequilibrium solvent response, equilibrium response in the ground and excited electronic states, as well as the cumulant and direct evaluation of the optical response function. In general, the linear response and cumulant approximations are found to hold, although minor deviations are found with all solvents. The ground state, linear response, and cumulant data show best agreement with experiment, most likely due to the better tested ground-state force field and the robust behavior of the linear response and cumulant approximations. The main conclusion of our earlier work explaining the weak solvent dependence by the domination of the van der Waals interaction component remains intact within the more advanced treatments. However, the molecular origin of this surprising experimental observation is different in water and chloroform compared to cyclohexane.