334 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
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
Microwave assisted low temperature synthesis of MnZn ferrite nanoparticles
MnZnFe2O4ferrite nanoparticles were prepared by co-precipitation method using a microwave heating system at temperature of 100 °C. X-ray diffraction reveals the samples as prepared are pure ferrite nanocrystalline phase, transmission electron microscopy image analysis shows particles are in agglomeration state with an average size of about 10 nm, furthermore, crystal size of samples are increased with longer microwave heating
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
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
Analysis of Mice Lacking DNaseI Hypersensitive Sites at the 5′ End of the IgH Locus
The 5′ end of the IgH locus contains a cluster of DNaseI hypersensitive sites, one of which (HS1) was shown to be pro-B cell specific and to contain binding sites for the transcription factors PU.1, E2A, and Pax5. These data as well as the location of the hypersensitive sites at the 5′ border of the IgH locus suggested a possible regulatory function for these elements with respect to the IgH locus. To test this notion, we generated mice carrying targeted deletions of either the pro-B cell specific site HS1 or the whole cluster of DNaseI hypersensitive sites. Lymphocytes carrying these deletions appear to undergo normal development, and mutant B cells do not exhibit any obvious defects in V(D)J recombination, allelic exclusion, or class switch recombination. We conclude that deletion of these DNaseI hypersensitive sites does not have an obvious impact on the IgH locus or B cell development
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