Molecular solvent-dynamical effects on activated electron-transfer kinetics: How important is solvent friction?

The likely extent of retardation exerted by solvent friction upon the rates of activated electron-transfer (ET) processes is explored and evaluated with reference to some extant solvent-dependent data for metallocene ET self exchanges. Barrier-crossing frequencies extracted from the experimental kinetic and barrier data for suitably adiabatic reactions are compared with solvent inertial frequencies (i.e. the zero-friction limit) as estimated from currently available analytic expressions. The additional extent of rate retardation seen in passing from low-friction to ostensibly strongly overdamped solvents, as deduced in this manner, is seen to be muted substantially in comparison with the predictions of conventional Debye-continuum approaches, although following a solvent functionality that is nevertheless roughly in accord with the latter. The likely importance of more rapid dynamics associated with short-range (molecular) solvation is addressed in the light of these findings.     

Uncharged isocoumarin-based inhibitors of urokinase-type plasminogen activator

Background  

Urokinase-type plasminogen activator (uPA) plays a major role in extracellular proteolytic events associated with tumor cell growth, migration and angiogenesis. Consequently, uPA is an attractive target for the development of small molecule active site inhibitors. Most of the recent drug development programs aimed at nonpeptidic inhibitors targeted at uPA have focused on arginino mimetics containing amidine or guanidine functional groups attached to aromatic or heterocyclic scaffolds. There is a general problem of limited bioavailability of these charged inhibitors. In the present study, uPA inhibitors were designed on an isocoumarin scaffold containing uncharged substituents.     

Entrainment and stimulated emission of ultrasonic piezoelectric auto-oscillators

Theoretical modeling and laboratory tests are conducted for nonlinear auto-oscillating piezoelectric ultrasonic devices coupled to reverberant elastic bodies. The devices are shown to exhibit behavior familiar from the theory of coupled auto-oscillators. In particular, these spontaneously emitting devices adjust their limit-cycle frequency to the spectrum of the body. It is further shown that the auto-oscillations can be entrained by an applied field; an incident wave at a frequency close to the frequency of the natural limit cycle entrains the oscillator. Special attention is paid to the phase of entrainment. Depending on details, the phase is such that the oscillator can be in a state of stimulated emission: the incident field amplifies the ultrasonic power emitted by the oscillator. These behaviors are essential to eventual design of an ultrasonic system that would consist of a number of such devices all synchronized to their mutual field, a system that would be an analog to a laser. A prototype uaser is constructed.     

Spectral functions at small energies and the electrical conductivity in hot quenched lattice QCD

In lattice QCD, the maximum entropy method can be used to reconstruct spectral functions from Euclidean correlators obtained in numerical simulations. We show that at finite temperature the most commonly used algorithm, employing Bryan's method, is inherently unstable at small energies and gives a modification that avoids this. We demonstrate this approach using the vector current-current correlator obtained in quenched QCD at finite temperature. Our first results indicate a small electrical conductivity above the deconfinement transition.     

Application of Mie theory to determine the structure of spheroidal scatterers in biological materials

We present here the results of a numerical study on light scattering from nonspherical particles with relevance to detecting precancerous states in epithelial tissues. In previous studies of epithelial cell nuclei, the experimental light scattering data have been analyzed by comparison with Mie theory. However, given the spheroidal shape of many cell nuclei, the validity of this assumption demands a thorough investigation. We investigate this assumption by using the T-matrix method to model light scattered from spheroids with parameters relevant to epithelial cell nuclei. In our previous studies, we have developed a data analysis procedure that extracts the oscillatory component of the angular-scattering distribution for an ensemble of epithelial cell nuclei for comparison with Mie theory. We demonstrate that application of our analysis procedure to the predictions of the T-matrix method for spheroids, oriented such that their axis of symmetry is aligned with the incident light propagation direction, generally yields the spheroid dimension that is transverse to the incident light propagation direction with subwavelength accuracy.     

On the Whitham system for the (2+1)-dimensional nonlinear Schrödinger equation

Whitham modulation equations are derived for the nonlinear Schrödinger equation in the plane ((2+1)-dimensional nonlinear Schrödinger [2d NLS]) with small dispersion. The modulation equations are obtained in terms of both physical and Riemann-type variables; the latter yields equations of hydrodynamic type. The complete 2d NLS Whitham system consists of six dynamical equations in evolutionary form and two constraints. As an application, we determine the linear stability of one-dimensional traveling waves. In both the elliptic and hyperbolic cases, the traveling waves are found to be unstable. This result is consistent with previous investigations of stability by other methods and is supported by direct numerical calculations.     

Polymersomes Prepared from Thermoresponsive Fluorescent Protein–Polymer Bioconjugates: Capture of and Report on Drug and Protein Payloads

Polymersomes provide a good platform for targeted drug delivery and the creation of complex (bio)catalytically active systems for research in synthetic biology. To realize these applications requires both spatial control over the encapsulation components in these polymersomes and a means to report where the components are in the polymersomes. To address these twin challenges, we synthesized the protein–polymer bioconjugate PNIPAM‐b‐amilFP497 composed of thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM) and a green‐fluorescent protein variant (amilFP497). Above 37 °C, this bioconjugate forms polymersomes that can (co‐)encapsulate the fluorescent drug doxorubicin and the fluorescent light‐harvesting protein phycoerythrin 545 (PE545). Using fluorescence lifetime imaging microscopy and Förster resonance energy transfer (FLIM‐FRET), we can distinguish the co‐encapsulated PE545 protein inside the polymersome membrane while doxorubicin is found both in the polymersome core and membrane.