Excited-state intermolecular proton transfer of firefly luciferin III. Proton transfer to a mild base

Steady-state and time-resolved techniques were employed to study the excited-state proton transfer (ESPT) from d-luciferin, the natural substrate of the firefly luciferase, to the mild acetate base in aqueous solutions. We found that in 1 M aqueous solutions of acetate or higher, a proton transfer (PT) process to the acetate takes place within 30 ps in both H(2)O and D(2)O solutions. The time-resolved emission signal is composed of three components. We found that the short-time component decay time is 300 and 600 fs in H(2)O and D(2)O, respectively. This component is attributed either to a PT process via the shortest water bridged complex available, ROH··H(2)O··Ac(-), or to PT taking place within a contact ion pair. The second time component of 2000 and 3000 fs for H(2)O and D(2)O, respectively, is attributed to ROH* acetate complex, whose proton wire is longer by one water molecule. The decay rate of the third, long-time component is proportional to the acetate concentration. We attribute it to the diffusion-assisted reaction as well as to PT process to the solvent.     

Exploring the functional interaction between POSH and ALIX and the relevance to HIV-1 release

Background

The ALG2-interacting protein X (ALIX)/AIP1 is an adaptor protein with multiple functions in intracellular protein trafficking that plays a central role in the biogenesis of enveloped viruses. The ubiquitin E3-ligase POSH (plenty of SH3) augments HIV-1 egress by facilitating the transport of Gag to the cell membrane. Recently, it was reported, that POSH interacts with ALIX and thereby enhances ALIX mediated phenotypes in Drosophila.

Results

In this study we identified ALIX as a POSH ubiquitination substrate in human cells: POSH induces the ubiquitination of ALIX that is modified on several lysine residues in vivo and in vitro. This ubiquitination does not destabilize ALIX, suggesting a regulatory function. As it is well established that ALIX rescues virus release of L-domain mutant HIV-1, HIV-1Δ_PTAP, we demonstrated that wild type POSH, but not an ubiquitination inactive RING finger mutant (POSH^V14A), substantially enhances ALIX-mediated release of infectious virions derived from HIV-1Δ_PTAP L-domain mutant (YPX_nL-dependent HIV-1). In further agreement with the idea of a cooperative function of POSH and ALIX, mutating the YPX_nL-ALIX binding site in Gag completely abrogated augmentation of virus release by overexpression of POSH. However, the effect of the POSH-mediated ubiquitination appears to be auxiliary, but not necessary, as silencing of POSH by RNAi does not disturb ALIX-augmentation of virus release.

Conclusion

Thus, the cumulative results identified ALIX as an ubiquitination substrate of POSH and indicate that POSH and ALIX cooperate to facilitate efficient virus release. However, while ALIX is obligatory for the release of YPX_nL-dependent HIV-1, POSH, albeit rate-limiting, may be functionally interchangeable.     

Gate‐Induced Modification of Water Adsorption on Dielectrics Probed by EFM and Carbon Nanotube FETs

Humidity plays an important role in molecular electronics. It facilitates charge movement on top of dielectric layers and modifies the device transfer characteristics. Using two different methods to probe temporal charge redistribution on the surface of dielectrics, we were able to extract the surface humidity for the first time. The first method is based on the relaxation time constants of the current through carbon nanotube field‐effect transistors (CNTFETs), and the second is based on electric force microscopy (EFM) measurements. Moreover, we found that applying external gate biases modifies the surface humidity. A theoretical model based on dielectrophoretic attraction between the water molecules and the substrate is introduced to explain this observation, and the results support our hypothesis. Furthermore, it is found that upon the adsorption of two to three layers of water the surface conductivity saturates.     

Ultra narrow PbS nanorods with intense fluorescence

We report on the narrowest "free" quantum rods of PbS with 1.7 nm diameter produced in a single step under bench-top reaction conditions. The nanorods exhibit molecule-like discrete narrow optical behavior with high fluorescence quantum yield. We propose a new macroscopic vortex assembly formation by simple spin casting route. Interestingly, the pattern generates fluorescence along its line from the nanorod domains. The ultra narrow nanorods with strong discrete fluorescence and robust stability could be useful in biological labeling, fluorescence resonance energy transfer, and optoelectronics applications, as well as to verify the theories in the very strong confinement regime.     

Interaction of scanning probes with semiconductor nanocrystals; physical mechanism and basis for near-field optical imaging

We investigate the modification of photoluminescence (PL) from single semiconductor nanocrystal quantum dots (NCs) in the proximity of metal and semiconducting atomic force microscope (AFM) tips. The presence of the tip alters the radiative decay rate of an emitter via interference and opens efficient nonradiative decay channels via energy transfer to the tip material. These effects cause quenching (or enhancement) of the emitter's PL intensity as a function of its distance from the interacting tip. We take advantage of this highly distance-dependent effect to realize a contrast mechanism for high-resolution optical imaging. AFM tips are optimized as energy acceptors by chemical functionalization with InAs NCs to achieve optical resolution down to 30 nm. The presented experimental scheme offers high-resolution optical information while maintaining the benefits of traditional AFM imaging. We directly measure the PL intensity of single NCs as a function of the tip distance. Our results are in good agreement with calculations made by a classical theoretical model describing an oscillating dipole interacting with a planar mirror.     

Work allocation to stations with varying learning slopes and without buffers

In this paper, we address the problem of allocating the work elements, belonging to the products of a lot, to the stations of an assembly line so as to minimize the makespan. The lots that are processed on the assembly line are characterized by a low overall demand for each product. There is no buffer permitted in between the stations, and the line operates under learning. In particular, the stations’ learning slopes are assumed to be different. We present a procedure to determine the optimal assignments of the workload to the stations under learning variability and show that it considerably affects these assignments.     

A graph-theoretic approach for comparing dimensions of components in simply-graded algebras

Any simple group-grading of a finite dimensional complex algebra induces a natural family of digraphs. We prove that in a digraph without parallel edges, the number of pairs of vertices having a common in-neighbor or a common out-neighbor is at least the number of edges. We deduce that for any simple group-grading, the dimension of the trivial component is maximal.     

On minimum power connectivity problems

Given a (directed or undirected) graph with edge costs, the power of a node is the maximum cost of an edge leaving it, and the power of the graph is the sum of the powers of its nodes. Motivated by applications for wireless networks, we present polynomial and improved approximation algorithms, as well as inapproximability results, for some classic network design problems under the power minimization criteria. Our main result is for the problem of finding a min-power subgraph that contains k internally-disjoint vs-paths from every node v to a given node s: we give a polynomial algorithm for directed graphs and a logarithmic approximation algorithm for undirected graphs. In contrast, we will show that the corresponding edge-connectivity problems are unlikely to admit even a polylogarithmic approximation.     

On the transformation toughening of a crack along an interface between a shape memory alloy and an isotropic medium

In this study, a bilinear cohesive zone model is employed to describe the transformation toughening behavior of a slowly propagating crack along an interface between a shape memory alloy and a linear elastic or elasto-plastic isotropic material. Small scale transformation zones and plane strain conditions are assumed. The crack growth is numerically simulated within a finite element scheme and its transformation toughening is obtained by means of resistance curves. It is found that the choice of the cohesive strength t₀ and the stress intensity factor phase angle φ greatly influence the toughening behavior of the bimaterial. The presented methodology is generalized for the case of an interface crack between a fiber reinforced shape memory alloy composite and a linear elastic, isotropic material. The effect of the cohesive strength t₀, as well as the fiber volume fraction are examined.