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.     

Space-variant Pancharatnam-Berry phase optical elements with computer-generated subwavelength gratings

Space-variant Pancharatnam-Berry phase optical elements based on computer-generated subwavelength gratings are presented. By continuously controlling the local orientation and period of the grating we can achieve any desired phase element. We present a theoretical analysis and experimentally demonstrate a Pancharatnam-Berry phase-based diffraction grating for laser radiation at a wavelength of 10.6microm.     

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.     

Study of the membrane effect on turbulent mixing measurements in shock tubes

The effect of the thin membrane on the time evolution of the shock wave induced turbulent mixing between the two gases initially separated by it is investigated using two different sets of experiments. In the first set, in which a single-mode large-amplitude initial perturbation was studied, two gas combinations (air/SF and air/air) and two membrane thicknesses were used. The main conclusion of these experiments was that the tested membrane has a negligible effect on the evolution of the mixing zone, which evolves as predicted theoretically. In the second set, in which similar gas combinations and membrane thicknesses were used, small amplitude random-mode initial perturbation, caused by the membrane rupture, rather than the large amplitude single-mode initial perturbation used in the first set, was studied. The conclusions of these experiments were: (1) The membrane has a significant effect on the mixing zone during the initial stages of its growth. This has also been observed in the air/air experiment where theoretically no growth should exist. (2) The membrane effect on the late time evolution, where the mixing zone width has reached a relatively large-amplitude, was relatively small and in good agreement with full numerical simulations. The main conclusion from the present experiments is that the effect of the membrane is important only during the initial stages of the evolution (before the re-shock), when the perturbations have very small amplitudes, and is negligible when the perturbations reach relatively large amplitudes. Received 29 August 1998 / Accepted 25 December 1998     

Two-photon enhanced optogalvanic signal and population inversion

Two-photon enhancement of the optogalvanic signal is shown to be possible, both theoretically and experimentally, even in the case of population inversion of the first transition. This is shown, in particular, for the neon 1s₂ → 2p_i transitions.     

Geometric doppler effect: spin-split dispersion of thermal radiation

A geometric Doppler effect manifested by a spin-split dispersion relation of thermal radiation is observed. A spin-dependent dispersion splitting was obtained in a structure consisting of a coupled thermal antenna array. The effect is due to a spin-orbit interaction resulting from the dynamics of the surface waves propagating along the structure whose local anisotropy axis is rotated in space. The observation of the spin-symmetry breaking in thermal radiation may be utilized for manipulation of spontaneous or stimulated emission.     

From DNA to transistors

The rapid advance in molecular biology and nanotechnology opens up the possibility to explore the interface between biology and electronics at the single-molecule level. We focus on the organization of molecular electronic circuits. Interconnecting an immense number of molecular devices into a functional circuit and constructing a framework for integrated molecular electronics requires new concepts. A promising avenue relies on bottom-up assembly where the information for the circuit connectivity and functionality is embedded in the molecular building blocks. Biology can provide concepts and mechanisms for advancing this approach, but there is no straightforward way to apply them to electronics since biological molecules are essentially electrically insulating. Bridging the chasm between biology and electronics therefore presents great challenges. Circuit organization on the molecular scale is considered and contrasted with the levels of organization presented by the living world. The discussion then focuses on our proposal to harness DNA and molecular biology to construct the scaffold for integrated molecular electronics. DNA metallization is used to convert the DNA scaffold into a conductive one. We present the framework of sequence-specific molecular lithography based on the biological mechanism of homologous genetic recombination and carried out by the bacterial protein RecA. Molecular lithography enables us to use the information encoded in the scaffold DNA molecules for directing the construction of an electronic circuit. We show that it can lead all the way from DNA molecules to working transistors in a test-tube. Carbon nanotubes are incorporated as the active electronic components in the DNA-templated transistors. Our approach can, in principle, be applied to the fabrication of larger-scale electronic circuits. The realization of complex DNA-based circuits will, however, require new concepts and additional biological machinery allowing, for example, feedback from the electronic functionality to direct the assembly process and adaptation mechanisms.     

On parabolic induction on inner forms of the general linear group over a non-archimedean local field

We give new criteria for the irreducibility of parabolic induction on the general linear group and its inner forms over a local non-archimedean field. In particular, we give a necessary and sufficient condition when the inducing data is of the form \(\pi \otimes \sigma \) where \(\pi \) is a ladder representation and \(\sigma \) is an arbitrary irreducible representation. As an application we simplify the proof of the classification of the unitary dual.     

The structure of protonated diamines and polyamines

The reduced mobilities in air, at 200C, of six isomeric C₇H₁₈N₂ protonated diamines, two triamines (caldine and spermidine), and two tetramines (thermine and spermine) were measured by ion mobility spectrometric (IMS) techniques. The results indicated that all these polyamines undergo proton-induced cyclization, with the proton forming a bridge between two amino groups. It appears as if the favored configuration of the protonated polyamines involves a six- or seven-membered ring rather than a bridge between the terminal amino groups. It is believed that in the tetramines the cyclic structure is formed between the two central, more basic, secondary amine sites.