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At least 127 records · Page 7

The M2 Proton Channel of Influenza Virus: How Does It Work?

The transport of protons across membranes is an essential process for both bioenergetics of modem cells and the origins of cellular life. All living systems make use of proton gradients across cell walls to convert environmental energy into a high-energy chemical compound, adenosine triphosphate (ATR), synthesized from adenosine diphosphate. ATR, in turn, is used as a source of energy to drive many cellular reactions. The ubiquity of this process in biology suggests that even the earliest cellular systems were relying on proton gradient for harvesting environmental energy needed to support their survival and growth. In contemporary cells, proton transfer is assisted by large, complex proteins embedded in membranes. The issue addressed in this study was: how the same process can be accomplished with the aid of similar, but much simpler molecules that could have existed in the protobiological milieu? The model system used in the study contained a bilayer membrane made of phospholipid, dimyristoylphosphatidylcholine (DMPC), which is a good model of the biological membranes focusing cellular boundaries. Both sides of the bilayer were surrounded by water which simulated the environment inside and outside the cell. Embedded in the membrane was a fragment of the Influenza-A M2 protein and enough sodium counterions to maintain system neutrality. This protein has been shown to exhibit remarkably high rates of proton transport and, therefore, is an excellent model to study the formation of proton gradients across membranes. The Influenza M2 protein is 97 amino acids in length, but a fragment 25 amino acids long, which contains a transmembrane domain of 19 amino acids flanked by 3 amino acids on each side, is sufficient to transport protons. Four identical protein fragments, each folded into a helix, aggregate to form small channels spanning the membrane. Protons are conducted through a narrow pore in the middle of the channel in response to applied voltage. This channel is large enough to contain water molecules, and is normally filled with water. In analogy to the mechanism of proton transfer in some other channels, it has been postulated that protons are translocated along the network of water molecules filling the pore of the channel. This mechanism, however, must involve an additional, important step because the channel contains four histidine amino acid residues, one from each of the helices, which are sufficiently large to occlude the pore and interrupt the water network. The histidine residues ensure channel selectivity by blocking transport of small such as sodium or potassium. They have been also implicated in gating protons due to the ability of each histidine to become positively charged by accepting an additional proton. Two mechanisms of gating have been proposed. In one mechanism, all four histidines acquire an additional proton and, due to repulsion between their positive charges, move away from one another, thus opening the channel. The alternative mechanism relies of the ability of protons to move between different atoms in a molecule (tautomerization). Thus, a proton is captured on one side of the gate while another proton is released from the opposite side, and the molecule returns to the initial state through tautomerization. The simulations were designed to test these two mechanisms. Large-scale, atomic-level molecular dynamics simulations of the channel, in which the histidine residues were in different protonation states revealed that all intermediate states of the system involved in the tautomerization mechanism are structurally stable and the arrangement of water molecules in the channel is conducive to the proton transport. In contrast, in the four-protonated state, postulated to exist in the gate-opening mechanism, the electrostatic repulsion between the histidine residues appears to be so large that the channel looses its structural integrity and one helix moves away from the remaining three. This result indicates that such a mechanism of proton transport is unlikely. The simulations revealed that translocation along a network of water molecules in the channel and tautomerization of the histidine residues in the M2 proteins in the most likely mechanism of proton transport. The results not only explain how a remarkably simple protein system can efficiently aid in the formation of proton gradients across cell walls, but also suggest how this system can be genetically re-engineered to become a directional, reversible proton pump. Such a pump can provide energy to laboratory-built models of simple cellular systems. If they were successfully constructed it would greatly advance our understanding of the beginnings of life and find important applications in medicine and pharmacology.

Pohorille, Andrew↗

On the Nature of the Compact Object in SS 433. Observational Evidence of X-Ray Photon Index Saturation

We present an analysis of the X-ray spectral properties observed from black hole , candidate (BHC) binary SS 433. We have analyzed Rossi X-ray Time Explorer (RXTE) data from this source, coordinated with Green Bank Interferometer/RATAN-600. We show that SS 433 undergoes a X-ray spectral transition from the low hard state (LHS) to the intermediate state (IS). We show that the X-ray broad-band energy spectra during all spectral states are well fit by a sum of so called "Bulk Motion Comptonization (BMC) component" and by two (broad and narrow) Gaussians for the continuum and line emissions respectively. In addition to these spectral model components we also find a strong feature that we identify as a" blackbody-like (BB)" component which color temperature is in the range of 4-5 keV in 24 IS spectra during the radio outburst decay in SS 433. Our observational results on the "high temperature BB" bump leads us to suggest the presence of gravitationally redshifted annihilation line emission in this source. In fact this spectral feature has been recently reproduced in Monte Carlo simulations by Laurent and Titarchuk. We have also established the photon index saturation at about 2.3 in index vs mass accretion correlation. This index-mass accretion correlation allows us to evaluate the low limit of black hole (BH) mass of compact object in SS 433, M(sub bh) approximately > 2 solar masses, using the scaling method using BHC GX 339-4 as a reference source. Our estimate of the BH mass in SS 433 is consistent with recent BH mass measurement using the radial-velocity measurements of the binary system by Hillwig & Gies who find that M(sub x)( = (4.3 +/- 0.8) solar masses. This is the smallest BH mass found up to now among all BH sources. Moreover, the index saturation effect versus mass accretion rate revealed in SS 433, like in a number of other BH candidates, is the strong observational evidence for the presence of a BH in SS 433.

Seifina, Elena↗

Adapting algebraic diagrammatic construction schemes for the polarization propagator to problems with multi-reference electronic ground states exploiting the spin-flip ansatz

For the investigation of molecular systems with electronic ground states exhibiting multi-reference character, a spin-flip (SF) version of the algebraic diagrammatic construction (ADC) scheme for the polarization propagator up to third order perturbation theory (SF-ADC(3)) is derived via the intermediate state representation and implemented into our existing ADC computer program adcman. The accuracy of these new SF-ADC(n) approaches is tested on typical situations, in which the ground state acquires multi-reference character, like bond breaking of H{sub 2} and HF, the torsional motion of ethylene, and the excited states of rectangular and square-planar cyclobutadiene. Overall, the results of SF-ADC(n) reveal an accurate description of these systems in comparison with standard multi-reference methods. Thus, the spin-flip versions of ADC are easy-to-use methods for the calculation of “few-reference” systems, which possess a stable single-reference triplet ground state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectral state dependence of the 0.4–2 MeV polarized emission in Cygnus X-1 seen with INTEGRAL/IBIS, and links with the AMI radio data

Polarization of the ≳400 keV hard tail of the microquasar Cygnus X-1 has been independently reported by INTEGRAL/Imager on Board the INTEGRAL Satellite (IBIS), and INTEGRAL/SPectrometer on INTEGRAL and interpreted as emission from a compact jet. These conclusions were, however, based on the accumulation of all INTEGRAL data regardless of the spectral state. We utilize additional INTEGRAL exposure accumulated until 2012 December, and include the AMI/Ryle (15 GHz) radio data in our study. We separate the observations into hard, soft, and intermediate/transitional states and detect radio emission from a compact jet in hard and intermediate states (IS), but not in the soft. The 10–400 keV INTEGRAL (JEM-X and IBIS) state resolved spectra are well modeled with thermal Comptonization and reflection components. We detect a hard tail in the 0.4–2 MeV range for the hard state only. We extract the state dependent polarigrams of Cyg X-1, which are all compatible with no or an undetectable level of polarization except in the 400–2000 keV range in the hard state where the polarization fraction is 75% ± 32% and the polarization angle 40.°0 ± 14.°3. An upper limit on the 0.4–2 MeV soft state polarization fraction is 70%. Due to the short exposure, we obtain no meaningful constraint for the IS. The likely detection of a >400 keV polarized tail in the hard state, together with the simultaneous presence of a radio jet, reinforce the notion of a compact jet origin of the >400 keV emission.

79 ASTRONOMY AND ASTROPHYSICS↗

Spin-dependent tunneling recombination in heterostructures with a magnetic layer

We propose a mechanism for the generation of spin polarization in semiconductor heterostructures with a quantum well and a magnetic impurity layer spatially separated from it. The spin polarization of carriers in a quantum well originates from spin-dependent tunneling recombination at impurity states in the magnetic layer, which is accompanied by a fast linear increase in the degree of circular polarization of photoluminescence from the quantum well. Two situations are theoretically considered. In the first case, resonant tunneling to the spin-split sublevels of the impurity center occurs and spin polarization is caused by different populations of resonance levels in the quantum well for opposite spin projections. In the second, nonresonant case, the spin-split impurity level lies above the occupied states of electrons in the quantum well and plays the role of an intermediate state in the two-stage coherent spin-dependent recombination of an electron from the quantum well and a hole in the impurity layer. The developed theory allows us to explain both qualitatively and quantitatively the kinetics of photoexcited electrons in experiments with photoluminescence with time resolution in Mn-doped InGaAs heterostructures.

36 MATERIALS SCIENCE↗

Crystallographic snapshots of sulfur insertion by lipoyl synthase

Lipoyl synthase (LipA) catalyzes the insertion of two sulfur atoms at the unactivated C6 and C8 positions of a protein-bound octanoyl chain to produce the lipoyl cofactor. To activate its substrate for sulfur insertion, LipA uses a [4Fe-4S] cluster and S-adenosylmethionine (AdoMet) radical chemistry; the remainder of the reaction mechanism, especially the source of the sulfur, has been less clear. One controversial proposal involves the removal of sulfur from a second (auxiliary) [4Fe-4S] cluster on the enzyme, resulting in destruction of the cluster during each round of catalysis. Here, we present two high-resolution crystal structures of LipA from Mycobacterium tuberculosis: one in its resting state and one at an intermediate state during turnover. In the resting state, an auxiliary [4Fe-4S] cluster has an unusual serine ligation to one of the irons. After reaction with an octanoyllysine-containing 8-mer peptide substrate and 1 eq AdoMet, conditions that allow for the first sulfur insertion but not the second insertion, the serine ligand dissociates from the cluster, the iron ion is lost, and a sulfur atom that is still part of the cluster becomes covalently attached to C6 of the octanoyl substrate. Here, this intermediate structure provides a clear picture of iron–sulfur cluster destruction in action, supporting the role of the auxiliary cluster as the sulfur source in the LipA reaction and describing a radical strategy for sulfur incorporation into completely unactivated substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unfolding of the Villin Headpiece Domain: Revealing Structural Heterogeneity with Time‐Resolved X‐Ray Solution Scattering and Markov State Modeling

Understanding protein folding pathways is crucial to deciphering the principles of protein structure and function. Here, the unfolding dynamics of the 35‐residue villin headpiece (HP35) and a norleucine‐substituted variant (2F4K) using a combination of experimental and computational techniques is investigated. Time‐resolved X‐ray solution scattering coupled with equilibrium molecular dynamics simulations and Markov state modeling reveals distinct unfolding mechanisms between the two variants: HP35 and 2F4K. Specifically, HP35 exhibits a two‐state unfolding process, whereas an intermediate state is identified for the 2F4K mutant. A Markov state model constructed from simulations is used to map atomic‐level transitions to experimental observations, providing insights into the role of sequence variations in modulating folding pathways. The findings underscore the importance of integrating experimental and computational approaches to unravel protein unfolding mechanisms between heterogenous structural ensembles.

Nijhawan, Adam K. [Department of Chemistry Northwe↗

A comparison of weak-turbulence and particle-in-cell simulations of weak electron-beam plasma interaction

Quasilinear theory has long been used to treat the problem of a weak electron beam interacting with plasma and generating Langmuir waves. Its extension to weak-turbulence theory treats resonant interactions of these Langmuir waves with other plasma wave modes, in particular, ion-sound waves. These are strongly damped in plasma of equal ion and electron temperatures, as sometimes seen in, for example, the solar corona and wind. Weak turbulence theory is derived in the weak damping limit, with a term describing ion-sound wave damping then added. In this paper, we use the EPOCH particle-in-cell code to numerically test weak turbulence theory for a range of electron-ion temperature ratios. We find that in the cold ion limit, the results agree well, but for increasing ion temperature the three-wave resonance becomes broadened in proportion to the ion-sound wave damping rate. Additionally, we establish lower limits on the number of simulation particles needed to accurately reproduce the electron and wave distributions in their saturated states and to reproduce their intermediate states and time evolution. These results should be taken into consideration in, for example, simulations of plasma wave generation in the solar corona of Type III solar radio bursts from the corona to the solar wind and in weak turbulence investigations of ion-acoustic lines in the ionosphere.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Theory of interstellar medium diagnostics

The theoretical interpretation of observed interplanetary resonance luminescence patterns is used as one of the must promising methods to determine the state of the local interstellar medium (LISM). However, these methods lead to discrepant results that would be hard to understand in the framework of any physical LISM scenario. Assuming that the observational data are reliable, two possibilities which could help to resolve these discrepancies are discussed: (1) the current modeling of resonance luminescence patterns is unsatisfactory and has to be improved, and (2) the extrapolated interstellar parameters are not indicative of the unperturbed LISM state, but rather designate an intermediate state attained in the outer regions of the solar system. It is shown that a quantitative treatment of the neutral gas-plasma interaction effects in the interface between the heliospheric and the interstellar plasmas is of major importance for the correct understanding of the whole complex.

Fahr, H. J.↗

Time-resolved x-ray crystallography capture of a slow reaction tetrahydrofolate intermediate

Time-resolved crystallography is a powerful technique to elucidate molecular mechanisms at both spatial (angstroms) and temporal (picoseconds to seconds) resolutions. We recently discovered an unusually slow reaction at room temperature that occurs on the order of days: the in crystalline reverse oxidative decay of the chemically labile (6S)-5,6,7,8-tetrahydrofolate in complex with its producing enzyme Escherichia coli dihydrofolate reductase. Here, we report the critical analysis of a representative dataset at an intermediate reaction time point. A quinonoid-like intermediate state lying between tetrahydrofolate and dihydrofolate features a near coplanar geometry of the bicyclic pterin moiety, and a tetrahedral sp 3 C6 geometry is proposed based on the apparent mFo-DFc omit electron densities of the ligand. The presence of this intermediate is strongly supported by Bayesian difference refinement. Isomorphous Fo-Fo difference map and multi-state refinement analyses suggest the presence of end-state ligand populations as well, although the putative intermediate state is likely the most populated. A similar quinonoid intermediate previously proposed to transiently exist during the oxidation of tetrahydrofolate was confirmed by polarography and UV-vis spectroscopy to be relatively stable in the oxidation of its close analog tetrahydropterin. We postulate that the constraints on the ligand imposed by the interactions with the protein environment might be the origin of the slow reaction observed by time-resolved crystallography.

59 BASIC BIOLOGICAL SCIENCES↗

Magnetization Reversal of Permalloy Microparticles with the Configuration Anisotropy by Magnetic-Force Microscopy

Abstract—Magnetic force microscopy has been used to study the distribution of the magnetization in permalloy microparticles with a configurational anisotropy. The triangular particles with different degrees of concavity of the lateral sides have been studied. An analysis of the results enables us to state that the particles can be in several quasi-homogeneous stable states. It is shown that the particle magnetization reversal can occur both stepwise and also via an intermediate state in the dependence on the particle orientation. It is demonstrated that the quasi-homogeneous magnetization orientation in a particle can be changed by a magnetic-force microscope probe.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Study of the mechanism of muon-catalyzed t + t fusion reaction

The mechanism for the muon catalyzed fusion reaction t + t → {sup 4}He + 2n + 11.33 MeV is investigated. The model of the cascade reaction with {sup 5}He as an intermediate state is considered, both the ground and the first exited states being taken into account. The neutron energy spectrum measured in the recent experiment is compared with the Monte-Carlo-simulated one. Varying reaction parameters, we obtain optimum values for the relative weights of the {sup 5}He ground and excited states and for the excitation energy and width of the excited state.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Structural changes correlated with magnetic spin state isomorphism in the S 2 state of the Mn 4 CaO 5 cluster in the oxygen-evolving complex of photosystem II

The Mn 4 CaO 5 cluster in photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (S i , i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in the S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. As a result, such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unveiling the hidden structure of complex stochastic biochemical networks

Complex Markov models are widely used and powerful predictive tools to analyze stochastic biochemical processes. However, when the network of states is unknown, it is necessary to extract information from the data to partially build the network and estimate the values of the rates. The short-time behavior of the first-passage time distributions between two states in linear chains has been shown recently to behave as a power of time with an exponent equal to the number of intermediate states. For a general Markov model we derive the complete Taylor expansion of the first-passage time distribution between two arbitrary states. By combining algebraic methods and graph theory approaches it is shown that the first term of the Taylor expansion is determined by the shortest path from the initial state to the final state. When this path is unique, we prove that the coefficient of the first term can be written in terms of the product of the transition rates along the path. It is argued that the application of our results to first-return times may be used to estimate the dependence of rates on external parameters in experimentally measured time distributions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Dynamic heterogeneity in the folding/unfolding transitions of FiP35

Molecular dynamics simulations have become an important tool in studying protein dynamics over the last few decades. Atomistic simulations on the order of micro- to milliseconds are becoming feasible and are used to study the state-of-the-art experiments in atomistic detail. Yet, analyzing the high-dimensional-long-temporal trajectory data is still a challenging task and sometimes leads to contradictory results depending on the analyses. To reveal the dynamic aspect of the trajectory, here we propose a simple approach which uses a time correlation function matrix and apply to the folding/unfolding trajectory of FiP35 WW domain [Shaw et al., Science 330, 341 (2010)]. The approach successfully characterizes the slowest mode corresponding to the folding/unfolding transitions and determines the free energy barrier indicating that FiP35 is not an incipient downhill folder. The transition dynamics analysis further reveals that the folding/unfolding transition is highly heterogeneous, e.g., the transition path time varies by ∼100 fold. We identify two misfolded states and show that the dynamic heterogeneity in the folding/unfolding transitions originates from the trajectory being trapped in the misfolded and half-folded intermediate states rather than the diffusion driven by a thermal noise. The current results help reconcile the conflicting interpretations of the folding mechanism and highlight the complexity in the folding dynamics. This further motivates the need to understand the transition dynamics beyond a simple free energy picture using simulations and single-molecule experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fundamental Superconductivity of Nb films for Quantum Computing Application

Niobium is a widely accepted material for quantum computing device as well as superconducting radio frequency (SRF) technology. Superconducting niobium is a marginal type II superconductor which has a very narrow gap (~20-30 mT) of the mixed state at 2K, even showing the intermediate state (IMS) at the early stage of magnetic vortex penetration. Tremendous progress has been made in understanding the impact of the Nb surface and bulk superconductivities on SRF resonator performance. However, the effect of thin superconducting Nb films for quantum computing applications requires further examination. In this study, we explore the fundamental superconducting properties of various thin Nb films and compare them with respect to the energy relaxation time, T1, measured from superconducting qubit fabricated with these films. The Nb films are fabricated both with or without a surface protective layer that prevents the formation of lossy Nb2O5. Electromagnetic properties are characterized by means of bulk magnetization, electromagnetic transport, and dynamics of surface superconductivity. In addition, analytical electron microscopy is implemented to further connect the superconducting properties to microstructure.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Thermal stresses in chemically hardening elastic media with application to the molding process

A method has been formulated for the determination of thermal stresses in materials which harden in the presence of an exothermic chemical reaction. Hardening is described by the transformation of the material from an inviscid liquid-like state into an elastic solid, where intermediate states consist of a mixture of the two, in a ratio which is determined by the degree of chemical reaction. The method is illustrated in terms of an infinite slab cast between two rigid mold surfaces. It is found that the stress component normal to the slab surfaces vanishes in the residual state, so that removal of the slab from the mold leaves the remaining residual stress unchanged. On the other hand, the residual stress component parallel to the slab surfaces does not vanish. Its distribution is described as a function of the parameters of the hardening process.

Levitsky, M.↗