Photochemical electron transfer at fixed distance : a synthetic model of the photosynthetic primary process

A series of meso-phenyloctamethylporphyrins covalently bonded at the 4'phenyl position to quinones via rigid bicyclo[2.2.2]octane spacers were synthesized for the study of the dependence of electron transfer reaction rate on solvent, distance, temperature, and energy gap. A general and convergent synthesis was developed based on the condensation of ac-biladienes with masked quinonespacer-benzaldehydes. From picosecond fluorescence spectroscopy emission lifetimes were measured in seven solvents of varying polarity. Rate constants were determined to vary from 5.0x10⁹sec^-1 in N,N-dimethylformamide to 1.15x10¹⁰ Sec^-1 in benzene, and were observed to rise at most by about a factor of three with decreasing solvent polarity. Experiments at low temperature in 2-MTHF glass (77K) revealed fast, nearly temperature-independent electron transfer characterized by non-exponential fluorescence decays, in contrast to monophasic behavior in fluid solution at 298K. This example evidently represents the first photosynthetic model system not based on proteins to display nearly temperature-independent electron transfer at high temperatures (nuclear tunneling). Low temperatures appear to freeze out the rotational motion of the chromophores, and the observed nonexponential fluorescence decays may be explained as a result of electron transfer from an ensemble of rotational conformations. The nonexponentiality demonstrates the sensitivity of the electron transfer rate to the precise magnitude of the electronic matrix element, which supports the expectation that electron transfer is nonadiabatic in this system. The addition of a second bicyclooctane moiety (15 Å vs. 18 Å edge-to-edge between porphyrin and quinone) reduces the transfer rate by at least a factor of 500-1500. Porphyrinquinones with variously substituted quinones allowed an examination of the dependence of the electron transfer rate constant κ_ET on reaction driving force. The classical trend of increasing rate versus increasing exothermicity occurs from 0.7 eV≤ |ΔG^0'(R)| ≤ 1.0 eV until a maximum is reached (κ_ET = 3 x 10⁸ sec^-1 rising to 1.15 x 10¹⁰ sec^-1 in acetonitrile). The rate remains insensitive to ΔG⁰ for ~ 300 mV from 1.0 eV≤ |ΔG^0’(R)| ≤ 1.3 eV, and then slightly decreases in the most exothermic case studied (cyanoquinone, κ_ET = 5 x 10⁹ sec^-1).

Real-Time Bayesian Analysis of Ground Motion Envelopes for Earthquake Early Warning

Current earthquake early warning systems usually make magnitude and location predictions and send out a warning to the users based on those predictions. We describe an algorithm that assesses the validity of the predictions in real-time. Our algorithm monitors the envelopes of horizontal and vertical acceleration, velocity, and displacement. We compare the observed envelopes with the ones predicted by Cua & Heaton's envelope ground motion prediction equations (Cua 2005). We define a "test function" as the logarithm of the ratio between observed and predicted envelopes at every second in real-time. Once the envelopes deviate beyond an acceptable threshold, we declare a misfit. Kurtosis and skewness of a time evolving test function are used to rapidly identify a misfit. Real-time kurtosis and skewness calculations are also inputs to both probabilistic (Logistic Regression and Bayesian Logistic Regression) and nonprobabilistic (Least Squares and Linear Discriminant Analysis) models that ultimately decide if there is an unacceptable level of misfit. This algorithm is designed to work at a wide range of amplitude scales. When tested with synthetic and actual seismic signals from past events, it works for both small and large events.

A high-speed image sensing technique with adjustable frame rate based on an ordinary CCD

In the sinusoidal phase modulating interferometer technique, the high-speed CCD is necessary to detect the interference signals. The reason of ordinary CCD's low frame rate was analyzed, and a novel high-speed image sensing technique with adjustable frame rate based on ail ordinary CCD was proposed. And the principle of the image sensor was analyzed. When the maximum frequency and channel bandwidth were constant, a custom high-speed sensor was designed by using the ordinary CCD under the control of the special driving circuit. The frame rate of the ordinary CCD has been enhanced by controlling the number of pixels of every frame; therefore, the ordinary of CCD can be used as the high frame rate image sensor with small amount of pixels. The multi-output high-speed image sensor has the deficiencies of low accuracy, and high cost, while the high-speed image senor with small number of pixels by using this technique can overcome theses faults. The light intensity varying with time was measured by using the image sensor. The frame rate was LIP to 1600 frame per second (f/s), and the size of every frame and the frame rate were adjustable. The correlation coefficient between the measurement result and the standard values were higher than 0.98026, and the relative error was lower than 0.53%. The experimental results show that this sensor is fit to the measurements of sinusoidal phase modulating interferometer technique. (c) 2007 Elsevier GmbH. All rights reserved.

Motion simulation of annular polishing

Based on the Coulomb friction model, the frictional motion model of workpiece relating to the polishing pad was presented in annular polishing. By the dynamic analysis software, the model was simulated and analysed. The conclusions from the results were that the workpiece did not rotate steadily. When the angular velocity of ring and the direction were the same as that of the polishing pad, the angular velocity of workpiece hoicked at the beginning and at the later stage were the same as that of the polishing pad before contacting with the ring. The angular velocity of workpiece vibrated at the moment of contacting with the ring. After that the angular velocity of workpiece increased gradually and fluctuated at a given value, while the angular velocity of ring decreased gradually and also fluctuated at a given value. Since the contact between the workpiece and the ring was linear, their linear velocities and directions should be the same. But the angular velocity of workpiece was larger than that of the polishing pad on the condition that the radius of the workpiece was less than that of the ring. This did not agree with the pure translation principle and the workpiece surface could not be flat, either. Consequently, it needed to be controlled with the angular velocity of ring and the radii of the ring and the workpiece, besides friction to make the angular velocity of workpiece equal to that of the polishing pad for obtaining fine surface flatness of the workpiece. Copyright © 2007 Inderscience Enterprises Ltd.}

Structural capital, innovation capability, and company performance in technology-based colombian firms

[EN] In today s economy, innovation is considered to be one of the main driving forces behind business competitiveness, if not the most relevant one. Traditionally, the study of innovation has been addressed from different perspectives. Recently, literature on knowledge management and intellectual capital has provided new insights. Considering this, the aim of this paper is to analyze the impact of different organizational conditions i.e. structural capital on innovation capability and innovation performance, from an intellectual capital (IC) perspective. As regards innovation capability, two dimensions are considered: new idea generation and innovation project management. The population subject to study is made up of technology-based Colombian firms. In order to gather information about the relevant variables involved in the research, a questionnaire was designed and addressed to the CEOs of the companies making up the target population. The sample analyzed is made up of 69 companies and is large enough to carry out a statistical study based on structural equation modelling (partial least squares approach) using PLS-Graph software (Chin and Frye, 2003). The results obtained show that structural capital explains to a great extent both the effectiveness of the new idea generation process and of innovation project management. However, the influence of each specific organizational component making up structural capital (organizational design, organizational culture, hiring and professional development policies, innovation strategy, technological capital, and external structure) varies. Moreover, successful innovation project management is the only innovation capability dimension that exerts a significant impact on company performance.

Spatiotemporal segmentation based on two-dimensional spatiotemporal entropic thresholding

A novel spatiotemporal segmentation technique is further developed for extracting uncovered background and moving objects from the image sequences, then the following motion estimation is performed only on the regions corresponding to moving objects. The frame difference contrast (FCON) and local variance contrast (LCON), which are related to the temporal and spatial homogeneity of the image sequence, are selected to form the 2-D spatiotemporal entropy. Then the spatial segmentation threshold is determined by maximizing the 2-D spatiotemporal entropy, and the temporal segmentation point is selected to minimize the complexity measure for image sequence coding. Since both temporal and spatial correlation of an image sequence are exploited, this proposed spatiotemporal segmentation technique can further be used to determine the positions of reference frames adaptively, hence resulting in a low bit rate. Experimental results show that this segmentation-based coding scheme is more efficient than usual fixed-size coding algorithms. (C) 1997 Society of Photo-Optical Instrumentation Engineers.

Insights into mechanism kinematics for protein motion simulation

Background: The high demanding computational requirements necessary to carry out protein motion simulations make it difficult to obtain information related to protein motion. On the one hand, molecular dynamics simulation requires huge computational resources to achieve satisfactory motion simulations. On the other hand, less accurate procedures such as interpolation methods, do not generate realistic morphs from the kinematic point of view. Analyzing a protein's movement is very similar to serial robots; thus, it is possible to treat the protein chain as a serial mechanism composed of rotational degrees of freedom. Recently, based on this hypothesis, new methodologies have arisen, based on mechanism and robot kinematics, to simulate protein motion. Probabilistic roadmap method, which discretizes the protein configurational space against a scoring function, or the kinetostatic compliance method that minimizes the torques that appear in bonds, aim to simulate protein motion with a reduced computational cost. Results: In this paper a new viewpoint for protein motion simulation, based on mechanism kinematics is presented. The paper describes a set of methodologies, combining different techniques such as structure normalization normalization processes, simulation algorithms and secondary structure detection procedures. The combination of all these procedures allows to obtain kinematic morphs of proteins achieving a very good computational cost-error rate, while maintaining the biological meaning of the obtained structures and the kinematic viability of the obtained motion. Conclusions: The procedure presented in this paper, implements different modules to perform the simulation of the conformational change suffered by a protein when exerting its function. The combination of a main simulation procedure assisted by a secondary structure process, and a side chain orientation strategy, allows to obtain a fast and reliable simulations of protein motion.

Quantum Simulator for Transport Phenomena in Fluid Flows

Transport phenomena still stand as one of the most challenging problems in computational physics. By exploiting the analogies between Dirac and lattice Boltzmann equations, we develop a quantum simulator based on pseudospin-boson quantum systems, which is suitable for encoding fluid dynamics transport phenomena within a lattice kinetic formalism. It is shown that both the streaming and collision processes of lattice Boltzmann dynamics can be implemented with controlled quantum operations, using a heralded quantum protocol to encode non-unitary scattering processes. The proposed simulator is amenable to realization in controlled quantum platforms, such as ion-trap quantum computers or circuit quantum electrodynamics processors.

Energetics and Structural Characterization of the large-scale Functional Motion of Adenylate Kinase

Adenylate Kinase (AK) is a signal transducing protein that regulates cellular energy homeostasis balancing between different conformations. An alteration of its activity can lead to severe pathologies such as heart failure, cancer and neurodegenerative diseases. A comprehensive elucidation of the large-scale conformational motions that rule the functional mechanism of this enzyme is of great value to guide rationally the development of new medications. Here using a metadynamics-based computational protocol we elucidate the thermodynamics and structural properties underlying the AK functional transitions. The free energy estimation of the conformational motions of the enzyme allows characterizing the sequence of events that regulate its action. We reveal the atomistic details of the most relevant enzyme states, identifying residues such as Arg119 and Lys13, which play a key role during the conformational transitions and represent druggable spots to design enzyme inhibitors. Our study offers tools that open new areas of investigation on large-scale motion in proteins.

Electro-optic characteristics of a transparent nanophotonic device based on carbon nanotubes and liquid crystals.

We present electro-optic characteristics of a transparent nanophotonic device fabricated on quartz substrate based on multiwall carbon nanotubes and nematic liquid crystals (LCs). The nanotube electrodes spawn a Gaussian electric field to three dimensionally address the LC molecules. The electro-optic characteristics of the device were investigated to optimize the device performance and it was found that lower driving voltages were suitable for microlens array and phase modulation applications, while higher driving voltages with a holding voltage can be used for display-related applications.

Efficient block segmentation algorithm for true motion estimation

A block-based motion estimation technique is proposed which permits a less general segmentation performed using an efficient deterministic algorithm. Applied to image pairs from the Flower Garden and Table Tennis sequences, the algorithm successfully localizes motion discontinuities and detects uncovered regions. The algorithm is implemented in C on a Sun Sparcstation 20. The gradient-based motion estimation required 28.8 s CPU time, and 500 iterations of the segmentation algorithm required 32.6 s.

A procedure for automatically estimating model parameters in optical motion capture

Model-based optical motion capture systems require knowledge of the position of the markers relative to the underlying skeleton, the lengths of the skeleton's limbs, and which limb each marker is attached to. These model parameters are typically assumed and entered into the system manually, although techniques exist for calculating some of them, such as the position of the markers relative to the skeleton's joints. We present a fully automatic procedure for determining these model parameters. It tracks the 2D positions of the markers on the cameras' image planes and determines which markers lie on each limb before calculating the position of the underlying skeleton. The only assumption is that the skeleton consists of rigid limbs connected with ball joints. The proposed system is demonstrated on a number of real data examples and is shown to calculate good estimates of the model parameters in each. © 2004 Elsevier B.V. All rights reserved.

Segmentation and recognition using structure from motion point clouds

We propose an algorithm for semantic segmentation based on 3D point clouds derived from ego-motion. We motivate five simple cues designed to model specific patterns of motion and 3D world structure that vary with object category. We introduce features that project the 3D cues back to the 2D image plane while modeling spatial layout and context. A randomized decision forest combines many such features to achieve a coherent 2D segmentation and recognize the object categories present. Our main contribution is to show how semantic segmentation is possible based solely on motion-derived 3D world structure. Our method works well on sparse, noisy point clouds, and unlike existing approaches, does not need appearance-based descriptors. Experiments were performed on a challenging new video database containing sequences filmed from a moving car in daylight and at dusk. The results confirm that indeed, accurate segmentation and recognition are possible using only motion and 3D world structure. Further, we show that the motion-derived information complements an existing state-of-the-art appearance-based method, improving both qualitative and quantitative performance. © 2008 Springer Berlin Heidelberg.

Physiological modelling for improved reliability in silhouette-driven gradient-based hand tracking

We present a gradient-based motion capture system that robustly tracks a human hand, based on abstracted visual information - silhouettes. Despite the ambiguity in the visual data and despite the vulnerability of gradient-based methods in the face of such ambiguity, we minimise problems related to misfit by using a model of the hand's physiology, which is entirely non-visual, subject-invariant, and assumed to be known a priori. By modelling seven distinct aspects of the hand's physiology we derive prior densities which are incorporated into the tracking system within a Bayesian framework. We demonstrate how the posterior is formed, and how our formulation leads to the extraction of the maximum a posteriori estimate using a gradient-based search. Our results demonstrate an enormous improvement in tracking precision and reliability, while also achieving near real-time performance. © 2009 IEEE.

A vision-based remote control

This Chapter presents a vision-based system for touch-free interaction with a display at a distance. A single camera is fixed on top of the screen and is pointing towards the user. An attention mechanism allows the user to start the interaction and control a screen pointer by moving their hand in a fist pose directed at the camera. On-screen items can be chosen by a selection mechanism. Current sample applications include browsing video collections as well as viewing a gallery of 3D objects, which the user can rotate with their hand motion. We have included an up-to-date review of hand tracking methods, and comment on the merits and shortcomings of previous approaches. The proposed tracker uses multiple cues, appearance, color, and motion, for robustness. As the space of possible observation models is generally too large for exhaustive online search, we select models that are suitable for the particular tracking task at hand. During a training stage, various off-the-shelf trackers are evaluated. From this data differentmethods of fusing them online are investigated, including parallel and cascaded tracker evaluation. For the case of fist tracking, combining a small number of observers in a cascade results in an efficient algorithm that is used in our gesture interface. The system has been on public display at conferences where over a hundred users have engaged with it. © 2010 Springer-Verlag Berlin Heidelberg.