993 resultados para Xanthophyll cycle Mehler-peroxidase reaction
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A set of exact one-dimensional solutions to coupled nonlinear equations describing the propagation of a relativistic ultrashort circularly polarized laser pulse in a cold collisionless and bounded plasma where electrons have an initial velocity in the laser propagating direction is presented. The solutions investigated here are in the form of quickly moving envelop solitons at a propagation velocity comparable to the light speed. The features of solitons in both underdense and overdense plasmas with electrons having different given initial velocities in the laser propagating direction are described. It is found that the amplitude of solitons is larger and soliton width shorter in plasmas where electrons have a larger initial velocity. In overdense plasmas, soliton duration is shorter, the amplitude higher than that in underdense plasmas where electrons have the same initial velocity.
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Using an unperturbed scattering theory, the characteristics of H atom photoionization are studied respectively by a linearly- and by a circularly- polarized one-cycle laser pulse sequence. The asymmetry for photoelectrons in two directions opposite to each other is investigated. It is found that the asymmetry degree varies with the carrier-envelope (CE) phase, laser intensity, as well as the kinetic energy of photoelectrons. For the linear polarization, the maximal ionization rate varies with the CE phase, and the asymmetry degree varies with the CE phase in a sine-like pattern. For the circular polarization, the maximal ionization rate keeps constant for various CE phases, but the variation of asymmetry degree is still in a sine-like pattern.
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The photoelectron angular distributions (PADs) from above-threshold ionization of atoms irradiated by one-cycle laser pulses satisfy a scaling law. The scaling law denotes that the main features of the PADs are determined by four dimensionless parameters: (1) the ponderomotive number u(p) = U-p/hw, the ponderomotive energy U-p in units of laser photon energy; (2) the binding number E-b = E-b/h(w), the atomic binding energy E-b in units of laser photon energy; (3) the number of absorbed photons q; (4) the carrier-envelope phase phi(0), the phase of the carrier wave with respect to the envelope. We verify the scaling law by theoretical analysis and numerical calculation, compared to that in long-pulse case. A possible experimental test to verify the scaling law is suggested.
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[EN] A review focused on recent advances in intramolecular aza-Wittig reaction of phosphazenes with several carbonyl or analogous compounds is reported. Phosphazenes afford intramolecular aza-Wittig reaction with different groups within the molecule as aldehydes, ketones, esters, thioesters, amides, anhydrides and sulfimides. One of the most important applications of this reaction is the synthesis of a wide range of heterocyclic compounds, ranging from simple monocyclic compounds to complex polycyclic and macrocyclic systems.
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The signal recognition particle (SRP) and its receptor (SR) are universally conserved protein machineries that deliver nascent peptides to their proper destination. The SRP RNA is a universally conserved and essential component of SRP, which serves as the catalyst of the protein targeting cycle. The SRP RNA accelerates SRP-SR complex formation at the beginning of the protein targeting reaction, and triggers GTP hydrolysis and SRP-SR complex disassembly at the end. Here we combined biochemical and biophysical approaches to investigate the molecular mechanism of the functions of the SRP RNA. We found that two functional ends in the SRP RNA mediate distinct functions. The tetraloop end facilitates initial assembly of SRP and SR by mediating an electrostatic interaction with the Lys399 receptor, which ensures efficient and accurate substrate targeting. At the later stage of the SRP cycle, the SRP-SR complex relocalizes ~ 100 Angstrom to the 5,3-distal end of the RNA, a conformation crucial for GTPase activation and cargo handover. These results, combined with recent structural work, elucidate the functions of the SRP RNA during the protein targeting reaction.
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Home to hundreds of millions of souls and land of excessiveness, the Himalaya is also the locus of a unique seismicity whose scope and peculiarities still remain to this day somewhat mysterious. Having claimed the lives of kings, or turned ancient timeworn cities into heaps of rubbles and ruins, earthquakes eerily inhabit Nepalese folk tales with the fatalistic message that nothing lasts forever. From a scientific point of view as much as from a human perspective, solving the mysteries of Himalayan seismicity thus represents a challenge of prime importance. Documenting geodetic strain across the Nepal Himalaya with various GPS and leveling data, we show that unlike other subduction zones that exhibit a heterogeneous and patchy coupling pattern along strike, the last hundred kilometers of the Main Himalayan Thrust fault, or MHT, appear to be uniformly locked, devoid of any of the creeping barriers that traditionally ward off the propagation of large events. The approximately 20 mm/yr of reckoned convergence across the Himalaya matching previously established estimates of the secular deformation at the front of the arc, the slip accumulated at depth has to somehow elastically propagate all the way to the surface at some point. And yet, neither large events from the past nor currently recorded microseismicity nearly compensate for the massive moment deficit that quietly builds up under the giant mountains. Along with this large unbalanced moment deficit, the uncommonly homogeneous coupling pattern on the MHT raises the question of whether or not the locked portion of the MHT can rupture all at once in a giant earthquake. Univocally answering this question appears contingent on the still elusive estimate of the magnitude of the largest possible earthquake in the Himalaya, and requires tight constraints on local fault properties. What makes the Himalaya enigmatic also makes it the potential source of an incredible wealth of information, and we exploit some of the oddities of Himalayan seismicity in an effort to improve the understanding of earthquake physics and cipher out the properties of the MHT. Thanks to the Himalaya, the Indo-Gangetic plain is deluged each year under a tremendous amount of water during the annual summer monsoon that collects and bears down on the Indian plate enough to pull it away from the Eurasian plate slightly, temporarily relieving a small portion of the stress mounting on the MHT. As the rainwater evaporates in the dry winter season, the plate rebounds and tension is increased back on the fault. Interestingly, the mild waggle of stress induced by the monsoon rains is about the same size as that from solid-Earth tides which gently tug at the planets solid layers, but whereas changes in earthquake frequency correspond with the annually occurring monsoon, there is no such correlation with Earth tides, which oscillate back-and-forth twice a day. We therefore investigate the general response of the creeping and seismogenic parts of MHT to periodic stresses in order to link these observations to physical parameters. First, the response of the creeping part of the MHT is analyzed with a simple spring-and-slider system bearing rate-strengthening rheology, and we show that at the transition with the locked zone, where the friction becomes near velocity neutral, the response of the slip rate may be amplified at some periods, which values are analytically related to the physical parameters of the problem. Such predictions therefore hold the potential of constraining fault properties on the MHT, but still await observational counterparts to be applied, as nothing indicates that the variations of seismicity rate on the locked part of the MHT are the direct expressions of variations of the slip rate on its creeping part, and no variations of the slip rate have been singled out from the GPS measurements to this day. When shifting to the locked seismogenic part of the MHT, spring-and-slider models with rate-weakening rheology are insufficient to explain the contrasted responses of the seismicity to the periodic loads that tides and monsoon both place on the MHT. Instead, we resort to numerical simulations using the Boundary Integral CYCLes of Earthquakes algorithm and examine the response of a 2D finite fault embedded with a rate-weakening patch to harmonic stress perturbations of various periods. We show that such simulations are able to reproduce results consistent with a gradual amplification of sensitivity as the perturbing period get larger, up to a critical period corresponding to the characteristic time of evolution of the seismicity in response to a step-like perturbation of stress. This increase of sensitivity was not reproduced by simple 1D-spring-slider systems, probably because of the complexity of the nucleation process, reproduced only by 2D-fault models. When the nucleation zone is close to its critical unstable size, its growth becomes highly sensitive to any external perturbations and the timings of produced events may therefore find themselves highly affected. A fully analytical framework has yet to be developed and further work is needed to fully describe the behavior of the fault in terms of physical parameters, which will likely provide the keys to deduce constitutive properties of the MHT from seismological observations.
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<p>Since its discovery in 1896, the Buchner reaction has fascinated chemists for more than a century. The highly reactive nature of the carbene intermediates allows for facile dearomatization of stable aromatic rings, and provides access to a diverse array of cyclopropane and seven-membered ring architectures. The power inherent in this transformation has been exploited in the context of a natural product total synthesis and methodology studies.</p> <p>The total synthesis work details efforts employed in the enantioselective total synthesis of (+)-salvileucalin B. The fully-substituted cyclopropane within the core of the molecule arises from an unprecedented intramolecular Buchner reaction involving a highly functionalized arene and an -diazo--ketonitrile. An unusual retro-Claisen rearrangement of a complex late-stage intermediate was discovered on route to the natural product.</p> <p>The unique reactivity of -diazo--ketonitriles toward arene cyclopropanation was then investigated in a broader methodological study. This specific di-substituted diazo moiety possesses hitherto unreported selectivity in intramolecular Buchner reactions. This technology was enables the preparation of highly functionalized norcaradienes and cyclopropanes, which themselves undergo various ring opening transformations to afford complex polycyclic structures.</p> <p>Finally, an enantioselective variant of the intramolecular Buchner reaction is described. Various chiral copper and dirhodium catalysts afforded moderate stereoinduction in the cyclization event.</p>
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The effect of the mixing of pulsed two color fields on the generation of an isolated attosecond pulse has been systematically investigated. One main color is 800 nm and the other color (or secondary color) is varied from 1.2 to 2.4 mu m. This work shows that the continuum length behaves in a similar way to the behavior of the difference in the square of the amplitude of the strongest and next strongest cycle. As the mixing ratio is increased, the optimal wavelength for the extended continuum shifts toward shorter wavelength side. There is a certain mixing ratio of intensities at which the continuum length bifurcates, i.e., the existence of two optimal wavelengths. As the mixing ratio is further increased, each branch bifurcates again into two sub-branches. This 2D map analysis of the mixing ratio and the wavelength of the secondary field easily allows one to select a proper wavelength and the mixing ratio for a given pulse duration of the primary field. The study shows that an isolated sub-100 attosecond pulse can be generated mixing an 11 fs full-width-half-maximum (FWHM), 800 laser pulse with an 1840 nm FWHM pulse. Furthermore the result reveals that a 33 fs FWHM, 800 nm pulse can produce an isolated pulse below 200 as, when properly mixed. (c) 2008 Optical Society of America.
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By solving numerically the full Maxwell-Bloch equations without the slowly varying envelope approximation and the rotating-wave approximation, we investigate the effects of Lorentz local field correction (LFC) on the propagation properties of few-cycle laser pulse in a dense A-type three-level atomic medium. We find that: when the area of the input pulse is larger, split of pulse occurs and the number of the sub-pulses with LFC is larger than that without LFC; at the same distance, the time interval between the first sub-pulse and the second sub-pulse in the case without LFC is longer than that with LFC, the time of pulse appearing in the case without LFC is later than that in the case with LFC, and the two phenomena are more obvious with propagation distance increasing; time evolution rules of the populations of levels vertical bar 1 >, vertical bar 2 > and vertical bar 3 > in the two cases with and without LFC are much different. When the area of the input pulse is smaller, effects of LFC on time evolutions of the pulse and populations are remarkably smaller than those in the case of larger area pulse. (c) 2008 Elsevier B.V. All rights reserved.
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We investigate high-order harmonic emission and isolated attosecond pulse (IAP) generation in atoms driven by a two-colour multi-cycle laser field consisting of an 800 nm pulse and an infrared laser pulse at an arbitrary wavelength. With moderate laser intensity, an IAP of similar to 220 as can be generated in helium atoms by using two-colour laser pulses of 35 fs/800 nm and 46 fs/1150 nm. The discussion based on the three-step semiclassical model, and time-frequency analysis shows a clear picture of the high-order harmonic generation in the waveform-controlled laser field which is of benefit to the generation of XUV IAP and attosecond electron pulses. When the propagation effect is included, the duration of the IAP can be shorter than 200 as, when the driving laser pulses are focused 1 mm before the gas medium with a length between 1.5 mm and 2 mm.
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<p>One of the greatest challenges in science lies in disentangling causality in complex, coupled systems. This is illustrated no better than in the dynamic interplay between the Earth and life. The early evolution and diversification of animals occurred within a backdrop of global change, yet reconstructing the potential role of the environment in this evolutionary transition is challenging. In the 200 million years from the end-Cryogenian to the Ordovician, enigmatic Ediacaran fauna explored body plans, animals diversified and began to biomineralize, forever changing the ocean's chemical cycles, and the biological community in shallow marine ecosystems transitioned from a microbial one to an animal one.</p> <p>In the following dissertation, a multi-faceted approach combining macro- and micro-scale analyses is presented that draws on the sedimentology, geochemistry and paleontology of the rocks that span this transition to better constrain the potential environmental changes during this interval. </p> <p>In Chapter 1, the potential of clumped isotope thermometry in deep time is explored by assessing the importance of burial and diagenesis on the thermometer. Eocene- to Precambrian-aged carbonates from the Sultanate of Oman were analyzed from current burial depths of 350-5850 meters. Two end-member styles of diagenesis independent of burial depth were observed. </p> <p>Chapters 2, 3 and 4 explore the fallibility of the Ediacaran carbon isotope record and aspects of the sedimentology and geochemistry of the rocks preserving the largest negative carbon isotope excursion on record---the Shuram Excursion. Chapter 2 documents the importance of temperature, fluid composition and mineralogy on the delta 18-O min record and interrogates the bulk trace metal signal. Chapter 3 explores the spatial variability in delta 13-C recorded in the transgressive Johnnie Oolite and finds a north-to-south trend recording the onset of the excursion. Chapter 4 investigates the nature of seafloor precipitation during this excursion and more broadly. We document the potential importance of microbial respiratory reactions on the carbonate chemistry of the sediment-water interface through time.</p> <p>Chapter 5 investigates the latest Precambrian sedimentary record in carbonates from the Sultanate of Oman, including how delta 13-C and delta 34-S CAS vary across depositional and depth gradients. A new model for the correlation of the Buah and Ara formations across Oman is presented. Isotopic results indicate delta 13-C varies with relative eustatic change and delta 34-S CAS may vary in absolute magnitude across Oman.</p> <p>Chapter 6 investigates the secular rise in delta 18-Omin in the early Paleozoic by using clumped isotope geochemistry on calcitic and phosphatic fossils from the Cambrian and Ordovician. Results do not indicate extreme delta 18-O seawater depletion and instead suggest warmer equatorial temperatures across the early Paleozoic. </p>
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No abstract.
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<p>Pyrroloindoline and unnatural tryptophan motifs are important targets for synthesis based on their incorporation into a diverse array of biologically active natural products. Both types of alkaloids have also found applications as chiral catalysts and tryptophan derivatives are commonly employed as biological probes. On account of their applications, these frameworks have inspired the development of numerous enantioselective, catalytic reactions. In particular, the past few years have witnessed an impressive number of novel approaches for pyrroloindoline formation.</p> <p>The first project described herein involves our contribution to pyrroloindoline research. We have developed an (<i>R</i>)-BINOLSnCl<sub>4</sub>-catalyzed formal (3 + 2) cycloaddition reaction between 3-substituted indoles and 2-amidoacrylates that affords pyrroloindoline-2-carboxylates bearing an all-carbon quaternary center. Mechanistic studies have elucidated that the enantiodetermining step is a highly face-selective catalyst-controlled protonation reaction. The subsequent application of this asymmetric protonation strategy to the synthesis of a variety of enantioenriched tryptophan derivatives is also discussed.</p>
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<p>To explain the ^(26)Mg isotopic anomaly seen in meteorites (^(26)Al daughter) as well as the observation of 1809-keV rays in the interstellar medium (live decay of 26Al) one must know, among other things, the destruction rate of ^(26)Al. Properties of states in ^(27)Si just above the ^(26)Al + p mass were investigated to determine the destruction rate of ^(26)Al via the ^(26)Al(p,)^(27)Si reaction at astrophysical temperatures.</p> <p>Twenty micrograms of ^(26)Al were used to produce two types of Al_2O_3 targets by evaporation of the oxide. One was onto a thick platinum backing suitable for (p,) work, and the other onto a thin carbon foil for the (^3He,d) reaction.</p> <p>The ^(26)Al(p,)^(27)Si excitation function, obtained using a germanium detector and voltage-ramped target, confirmed known resonances and revealed new ones at 770, 847, 876, 917, and 928 keV. Possible resonances below the lowest observed one at E_p = 286 keV were investigated using the ^(26)Al(^3He,d)^(27)Si proton-transfer reaction. States in 27Si corresponding to 196- and 286-keV proton resonances were observed. A possible resonance at 130 keV (postulated in prior work) was shown to have a strength of w less than 0.02 eV.</p> <p>By arranging four large Nal detector as a 47 calorimeter, the 196-keV proton resonance, and one at 247 keV, were observed directly, having w = 55 9 and 10 5 eV, respectively.</p> <p>Large uncertainties in the reaction rate have been reduced. At novae temperatures, the rate is about 100 times faster than that used in recent model calculations, casting some doubt on novae production of galactic ^(26)Al.</p>
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The asymmetric photoionization of atoms irradiated by intense, few-cycle laser pulses is studied numerically. The results show that the pulse intensity affects the asymmetric photoionization in three aspects. First, at higher intensities, the asymmetry becomes distinctive for few-cycle pulses of longer durations. Second, as the laser intensity increases, the maximal asymmetry first decreases then increases after it has reached a minimal value. Last, the value of the carrier-envelope phase corresponding to the maximal asymmetry varies with the pulse intensity. This study reveals that the increasing of pulse intensity is helpful for observing the asymmetric photoionization.