248 research outputs found
A Multi-Instrument Investigation of the Frequency Stability of Oscillations Above the Acoustic Cut-Off Frequency with Solar Activity
Below the acoustic cut-off frequency, oscillations are trapped within the
solar interior and become resonant. However, signatures of oscillations persist
above the acoustic cut-off frequency, and these travelling waves are known as
pseudomodes. Acoustic oscillation frequencies are known to be correlated with
the solar cycle, but the pseudomode frequencies are predicted to vary in
anti-phase. We have studied the variation in pseudomode frequencies with time
systematically through the solar cycle. We analyzed Sun-as-a-star data from
Variability of Solar Irradiance and Gravity Oscillations (VIRGO), and Global
Oscillations at Low Frequencies (GOLF), as well as the decomposed data from
Global Oscillation Network (GONG) for harmonic degrees . The
data cover over two solar cycles (1996--2021, depending on instrument). We
split them into overlapping 100-day long segments and focused on two frequency
ranges, namely -- and --. The
frequency shifts between segments were then obtained by fitting the
cross-correlation function between the segments' periodograms. For VIRGO and
GOLF, we found no significant variation of pseudomode frequencies with solar
activity. However, in agreement with previous studies, we found that the
pseudomode frequency variations are in anti-phase with the solar cycle for GONG
data. Furthermore, the pseudomode frequency shifts showed a double-peak feature
at their maximum, which corresponds to solar activity minimum, and is not seen
in solar activity proxies. An, as yet unexplained, pseudo-periodicity in the
amplitude of the variation with harmonic degree is also observed in the
GONG data
How Does BBr\u3csub\u3e3\u3c/sub\u3e Cyclize \u3ci\u3eo\u3c/i\u3e-Alkynylanisoles to Form Benzofurans?
Nature provides us with a wide array of chemicals that have beneficial uses. Cyclization reactions are important in the man-made creation of these chemicals. Past research by S3 scholar Samantha Ellis in Prof. Korich\u27s lab showed an unexpected cyclization reaction with o-alkynylanisoles in the presence of BBr3 instead of the expected ether cleavage reaction. We sought to understand this unusual reactivity using computational chemistry by comparing the energies of these competing pathways. However, we discovered that previously considered mechanisms for BBr3 assisted ether cleavage are incomplete. In this work we present an alternative mechanism for ether cleavage that has implications in a number of different reactions involving boron-containing reagents
Maple-Swarm: programming collective behavior for ensembles by extending HTN-planning
Programming goal-oriented behavior in collective adaptive systems is complex, requires high effort, and is failure-prone. If the system's user wants to deploy it in a real-world environment, hurdles get even higher: Programs urgently require to be situation-aware. With our framework Maple, we previously presented an approach for easing the act of programming such systems on the level of particular robot capabilities. In this paper, we extend our approach for ensemble programming with the possibility to address virtual swarm capabilities encapsulating collective behavior to whole groups of agents. By using the respective concepts in an extended version of hierarchical task networks and by adapting our self-organization mechanisms for executing plans resulting thereof, we can achieve that all agents, any agent, any other set of agents, or a swarm of agents execute (swarm) capabilities. Moreover, we extend the possibilities of expressing situation awareness during planning by introducing planning variables that can get modified at design-time or run-time as needed. We illustrate the possibilities with examples each. Further, we provide a graphical front-end offering the possibility to generate mission-specific problem domain descriptions for ensembles including a lightweight simulation for validating plans
Ether Cleavage Re-Investigated: Elucidating the Mechanism of BBr3- Facilitated Demethylation of Aryl Methyl Ethers
Boron tribromide is a versatile reagent utilized in diverse areas ranging from polymer chemistry to natural product synthesis.[1] Owing its high reactivity to the Lewis acidic boron center, BBr3 reactions include haloborylation,[2] boron–silicon exchange,[3] and rearrangement of 7,7-diphenylhydromorphone derivatives.[4] While there is no shortage in the diversity of BBr3-mediated reactions, many of the mechanisms for these transformations have not been fully elucidated. In this report we investigate the mechanism of ether cleavage by BBr3 [5–10] in anisole. Conceptually, demethylation of anisole is initiated by the formation of an ether adduct 1 followed by the loss of bromide. Free bromide nucleophilically attacks the methyl group of the cationic intermediate (2) cleaving the C–O bond and producing PhOBBr2, which undergoes hydrolysis upon aqueous work-up. While this pathway (Scheme 1) at first appears to be viable, we calculated that the formation of 2 and bromide in dichloromethane is thermodynamically inaccessible (ΔG = +38.9 kcal/mol). Recently, alternative mechanisms for ether cleavage were proposed by Sousa and Silva that involve unimolecular or bimolecular rate-determining steps that circumvent formation of bromide in solution (Scheme 2).[11] While a unimolecular process is kinetically favored for ethers containing one or more substituents (e.g. branched alkyl) that stabilize carbocation character in an SN1-like transition state, this barrier for demethylation of primary C atoms, like in the
methyl group of anisole, lies too high on the potential energy surface to be accessible under reported reaction conditions. They found that a bimolecular process (Scheme 2, bottom) decreases the kinetic barrier for anisole demethylation significantly. During this reaction pathway, one of the bromides of the first ether adduct nucleophilically attacks the methyl group of the second ether adduct. This is analogous to an SN2 reaction with 180o attack of the methyl group by a bromide in the nucleophilic ether adduct. However, this bimolecular pathway produces two highly charged intermediates 2 and 3 that Sousa and Silva did not investigate. Their computational investigation stopped with the calculation of the initial kinetic barrier.[11] We speculate that these charged intermediates may undergo a similar bimolecular reaction to yield two equivalents of PhOBBr2 and MeBr. Moreover, if charged intermediates are formed then we believe an important set of mechanistic pathways may have been overlooked, namely, those where Lewis acidic BBr3 abstracts bromide from the ether complex to form BBr4 – in a mechanism related to the pathway introduced in Scheme 1
Spatial and topological organization of DNA chains induced by gene co-localization
Transcriptional activity has been shown to relate to the organization of
chromosomes in the eukaryotic nucleus and in the bacterial nucleoid. In
particular, highly transcribed genes, RNA polymerases and transcription factors
gather into discrete spatial foci called transcription factories. However, the
mechanisms underlying the formation of these foci and the resulting topological
order of the chromosome remain to be elucidated. Here we consider a
thermodynamic framework based on a worm-like chain model of chromosomes where
sparse designated sites along the DNA are able to interact whenever they are
spatially close-by. This is motivated by recurrent evidence that there exists
physical interactions between genes that operate together. Three important
results come out of this simple framework. First, the resulting formation of
transcription foci can be viewed as a micro-phase separation of the interacting
sites from the rest of the DNA. In this respect, a thermodynamic analysis
suggests transcription factors to be appropriate candidates for mediating the
physical interactions between genes. Next, numerical simulations of the polymer
reveal a rich variety of phases that are associated with different topological
orderings, each providing a way to increase the local concentrations of the
interacting sites. Finally, the numerical results show that both
one-dimensional clustering and periodic location of the binding sites along the
DNA, which have been observed in several organisms, make the spatial
co-localization of multiple families of genes particularly efficient.Comment: Figures and Supplementary Material freely available on
http://dx.doi.org/10.1371/journal.pcbi.100067
JetCurry I. Reconstructing three-dimensional jet geometry from two-dimensional images
We present a three-dimensional (3-D) visualization of jet geometry using numerical methods based on a Markov Chain Monte Carlo (MCMC) and limited memory Broyden–Fletcher–Goldfarb–Shanno (BFGS) optimized algorithm. Our aim is to visualize the 3-D geometry of an active galactic nucleus (AGN) jet using observations, which are inherently two-dimensional (2-D) images. Many AGN jets display complex structures that include hotspots and bends. The structure of these bends in the jet’s frame may appear quite different than what we see in the sky frame, where it is transformed by our particular viewing geometry. The knowledge of the intrinsic structure will be helpful in understanding the appearance of the magnetic field and hence emission and particle acceleration processes over the length of the jet. We present the JetCurry algorithm to visualize the jet’s 3-D geometry from its 2-D image. We discuss the underlying geometrical framework and outline the method used to decompose the 2-D image. We report the results of our 3-D visualization of the jet of M87, using the test case of the knot D region. Our 3-D visualization is broadly consistent with the expected double helical magnetic field structure of knot D region of the jet. We also discuss the next steps in the development of the JetCurry algorithm
X-ray emission during the muonic cascade in hydrogen
We report our investigations of X rays emitted during the muonic cascade in
hydrogen employing charge coupled devices as X-ray detectors. The density
dependence of the relative X-ray yields for the muonic hydrogen lines (K_alpha,
K_beta, K_gamma) has been measured at densities between 0.00115 and 0.97 of
liquid hydrogen density. In this density region collisional processes dominate
the cascade down to low energy levels. A comparison with recent calculations is
given in order to demonstrate the influence of Coulomb deexcitation.Comment: 5 pages, Tex, 4 figures, submitted to Physical Review Letter
Targeted Deficiency of the Transcriptional Activator Hnf1α Alters Subnuclear Positioning of Its Genomic Targets
DNA binding transcriptional activators play a central role in gene-selective regulation. In part, this is mediated by targeting local covalent modifications of histone tails. Transcriptional regulation has also been associated with the positioning of genes within the nucleus. We have now examined the role of a transcriptional activator in regulating the positioning of target genes. This was carried out with primary β-cells and hepatocytes freshly isolated from mice lacking Hnf1α, an activator encoded by the most frequently mutated gene in human monogenic diabetes (MODY3). We show that in Hnf1a−/− cells inactive endogenous Hnf1α-target genes exhibit increased trimethylated histone H3-Lys27 and reduced methylated H3-Lys4. Inactive Hnf1α-targets in Hnf1a−/− cells are also preferentially located in peripheral subnuclear domains enriched in trimethylated H3-Lys27, whereas active targets in wild-type cells are positioned in more central domains enriched in methylated H3-Lys4 and RNA polymerase II. We demonstrate that this differential positioning involves the decondensation of target chromatin, and show that it is spatially restricted rather than a reflection of non-specific changes in the nuclear organization of Hnf1a-deficient cells. This study, therefore, provides genetic evidence that a single transcriptional activator can influence the subnuclear location of its endogenous genomic targets in primary cells, and links activator-dependent changes in local chromatin structure to the spatial organization of the genome. We have also revealed a defect in subnuclear gene positioning in a model of a human transcription factor disease
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