Proton Pumping in Cytochrome c Oxidase

Cytochrome c oxidase (CcO) is a large trans-membrane protein, which is the final enzyme in the respiratory electron transport chain in mitochondria or aerobic bacteria. It implements proton pumping through the mitochondrial membrane against the electrochemical gradient, by utilizing the chemical energy released by reducing O2 to water. The active site of the chemical reaction is called the Binuclear Center (BNC) that is made up of heme a3, CuB, a Tyrosine residue and their ligands. The protein is reduced four times by electron from cytochromes c to reduce O2 and to generate four different BNC redox states step by step. In each reduction step a proton is delivered to the BNC and another proton is pumped across the protein to increase the trans-membrane proton gradient. In CcO, the pumped proton is firstly located in the proton loading site (PLS), and then is released out of the protein. In these processes, a high conserved Glutamate residue, plays an essential role on the proton translocation either to the BNC or the PLS. In this thesis, Multi-Conformational Continuum Electrostatics (MCCE) and Molecular Dynamics (MD) are combined to study the proton affinity (pKa) of the high conserved Glutamate residue and the identity of the PLS. This Glutamate residue is located in a hydrophobic cavity in the protein, and the simulations show that the hydration of the cavity is controlled by the protonation state of the propionic acid of heme a3, a group on the proton outlet pathway. The changes in hydration and electrostatic interactions lower the proton affinity by at least 5 kcal/mol. The identity of the residues in the PLS is another open question in CcO research, and various groups above the BNC have been considered as candidates. We designed a new model for the simulation via separating the catalytic cycle into smaller substates and monitoring the charge of all residues in the protein. The results demonstrates the PLS is a cluster rather than a single residue, and the proton affinity of the heme a3 propionic acids primarily determines the number of protons loaded into the PLS

A Wideband and Polarization-Independent Metasurface Based on Phase Optimization for Monostatic and Bistatic Radar Cross Section Reduction

A broadband and polarization-independent metasurface is analyzed and designed for both monostatic and bistatic radar cross section (RCS) reduction in this paper. Metasurfaces are composed of two types of electromagnetic band-gap (EBG) lattice, which is a subarray with “0” or “” phase responses, arranged in periodic and aperiodic fashions. A new mechanism is proposed for manipulating electromagnetic (EM) scattering and realizing the best reduction of monostatic and bistatic RCS by redirecting EM energy to more directions through controlling the wavefront of EMwave reflected from the metasurface. Scattering characteristics of two kinds of metasurfaces, periodic arrangement and optimized phase layout, are studied in detail. Optimizing phase layout through particle swarm optimization (PSO) together with far field pattern prediction can produce a lot of scattering lobes, leading to a great reduction of bistatic RCS. For the designed metasurface based on optimal phase layout, a bandwidth of more than 80% is achieved at the normal incidence for the −9.5 dB RCS reduction for both monostatic and bistatic. Bistatic RCS reduction at frequency points with exactly 180∘ phase difference reaches 17.6 dB. Both TE and TM polarizations for oblique incidence are considered. The measured results are in good agreement with the corresponding simulations

Ultra-wideband, Wide Angle and Polarization-insensitive Specular Reflection Reduction by Metasurface based on Parameteradjustable Meta-Atoms

In this paper, an ultra-wideband, wide angle and polarization-insensitive metasurface is designed, fabricated, and characterized for suppressing the specular electromagnetic wave reflection or backward radar cross section (RCS). Square ring structure is chosen as the basic meta-atoms. A new physical mechanism based on size adjustment of the basic meta-atoms is proposed for ultra-wideband manipulation of electromagnetic (EM) waves. Based on hybrid array pattern synthesis (APS) and particle swarm optimization (PSO) algorithm, the selection and distribution of the basic meta-atoms are optimized simultaneously to obtain the ultra-wideband diffusion scattering patterns. The metasurface can achieve an excellent RCS reduction in an ultra-wide frequency range under x- and y-polarized normal incidences. The new proposed mechanism greatly extends the bandwidth of RCS reduction. The simulation and experiment results show the metasurface can achieve ultra-wideband and polarization insensitive specular reflection reduction for both normal and wide-angle incidences. The proposed methodology opens up a new route for realizing ultra-wideband diffusion scattering of EM wave, which is important for stealth and other microwave applications in the future

Performing group-level functional image analyses based on homologous functional regions mapped in individuals

Functional MRI (fMRI) studies have traditionally relied on intersubject normalization based on global brain morphology, which cannot establish proper functional correspondence between subjects due to substantial intersubject variability in functional organization. Here, we reliably identified a set of discrete, homologous functional regions in individuals to improve intersubject alignment of fMRI data. These functional regions demonstrated marked intersubject variability in size, position, and connectivity. We found that previously reported intersubject variability in functional connectivity maps could be partially explained by variability in size and position of the functional regions. Importantly, individual differences in network topography are associated with individual differences in task-evoked activations, suggesting that these individually specified regions may serve as the localizer to improve the alignment of task-fMRI data. We demonstrated that aligning task-fMRI data using the regions derived from resting state fMRI may lead to increased statistical power of task-fMRI analyses. In addition, resting state functional connectivity among these homologous regions is able to capture the idiosyncrasies of subjects and better predict fluid intelligence (gF) than connectivity measures derived from group-level brain atlases. Critically, we showed that not only the connectivity but also the size and position of functional regions are related to human behavior. Collectively, these findings suggest that identifying homologous functional regions across individuals can benefit a wide range of studies in the investigation of connectivity, task activation, and brain-behavior associations. Author summary No two individuals are alike. The size, shape, position, and connectivity patterns of brain functional regions can vary drastically between individuals. While interindividual differences in functional organization are well recognized, to date, standard procedures for functional neuroimaging research still rely on aligning different subjects' data to a nominal average brain based on global brain morphology. We developed an approach to reliably identify homologous functional regions in each individual and demonstrated that aligning data based on these homologous functional regions can significantly improve the study of resting state functional connectivity, task-fMRI activations, and brain-behavior associations. Moreover, we showed that individual differences in size, position, and connectivity of brain functional regions are dissociable, and each can provide nonredundant information in explaining human behavior

Exploring the Influence of Attitudes to Walking and Cycling on Commute Mode Choice Using a Hybrid Choice Model

Transport-related problems, such as automobile dependence, traffic congestion, and greenhouse emissions, lead to a great burden on the environment. In developing countries like China, in order to improve the air quality, promoting sustainable travel modes to reduce the automobile usage is gradually recognized as an emerging national concern. Though there are many studies related to the physically active modes (e.g., walking and cycling), the research on the influence of attitudes to active modes on travel behavior is limited, especially in China. To fill up this gap, this paper focuses on examining the impact of attitudes to walking and cycling on commute mode choice. Using the survey data collected in China cities, an integrated discrete choice model and the structural equation model are proposed. By applying the hybrid choice model, not only the role of the latent attitude played in travel mode choice, but also the indirect effects of social factors on travel mode choice are obtained. The comparison indicates that the hybrid choice model outperforms the traditional model. This study is expected to provide a better understanding for urban planners on the influential factors of green travel modes. Document type: Articl

Birational cobordism invariance of uniruled symplectic manifolds

A symplectic manifold $(M,\omega)$ is called {\em (symplectically) uniruled} if there is a nonzero genus zero GW invariant involving a point constraint. We prove that symplectic uniruledness is invariant under symplectic blow-up and blow-down. This theorem follows from a general Relative/Absolute correspondence for a symplectic manifold together with a symplectic submanifold. A direct consequence is that symplectic uniruledness is a symplectic birational invariant. Here we use Guillemin and Sternberg's notion of cobordism as the symplectic analogue of the birational equivalence.Comment: To appear in Invent. Mat

Exciton-phonon interaction in quasi-two dimensional layered (PEA)2(CsPbBr3)n-1PbBr4 perovskite.

Two-dimensional (2D) Ruddlesden-Popper perovskites with bulky organic cations have attracted extensive attention in light-emitting devices and photovoltaics due to their robust environment stability, tunable luminescent color, strong exciton binding and promising efficiency. A quantum well (QW) structure is spontaneously formed by sandwiching PbBr4 layers into bulky organic cations. However, some intrinsic excitonic mechanisms in these materials still need to be elucidated. In this study, the exciton-phonon interaction of quasi-2D (PEA)2(CsPbBr3)n-1PbBr4 with different PbBr4 layer numbers (n) was analyzed by temperature-varied photoluminescence (PL), scanning electron microscopy (SEM) and powder X-ray diffraction (PXRD). The mechanism of bandgap shifting with temperature was found to be dominated by the thermal expansion effect in the large-n 2D and bulk perovskite, and gradually switched to exciton-phonon interaction in the n = 1 (PEA)2PbBr4 phase, indicating enhanced exciton-phonon interaction in the thinner quantum well structure. Further analysis showed that the enhanced exciton-phonon interaction originated from the longitudinal optical phonon-exciton Fröhlich interaction rather than acoustic phonon-exciton coupling. We believe that our results will benefit the further optimization of light-emitting devices based on 2D perovskites