1,087 research outputs found
Phosphate Tether-Mediated Ring-Closing Metathesis Studies to Complex 1,3-anti-Diol-Containing Subunits
This is the peer reviewed version of the following article: Chegondi, R., Maitra, S., Markley, J. L., & Hanson, P. R. (2013). Phosphate Tether-Mediated Ring-Closing Metathesis Studies to Complex 1,3-anti-Diol-Containing Subunits. Chemistry (Weinheim an Der Bergstrasse, Germany), 19(25), 10.1002/chem.201300913. http://doi.org/10.1002/chem.201300913, which has been published in final form at doi.org/10.1002/chem.201300913. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.An array of examples of diastereoselective, phosphate tether-mediated ring-closing metathesis reactions, which highlight the importance of product ring size and substrate stereochemical compatibility, as well as complexity, is reported. Studies focus primarily on the formation of bicyclo[n.3.1]phosphates, involving the coupling of C2-symmetric dienediol subunits with a variety of simple, as well as complex alcohol cross-partners
Phosphate Tether-Mediated Ring-Closing Metathesis for the Generation of Medium to Large, P-Stereogenic Bicyclo[n.3.1]phosphates
A phosphate tether-mediated ring-closing metathesis study towards the synthesis of P-stereogenic bicyclo[6.3.1]-, bicyclo[7.3.1]-, and bicyclo[8.3.1]phosphates is reported. This study demonstrates expanded utility of phosphate tether-mediated desymmetrization of C2-symmetric, 1,3-anti-diol dienes in generating complex medium to large, P-stereogenic bicyclo[n.3.1]phosphates.
Anisotropic Brane Cosmology with Variable and
In this work, the cosmological implications of brane world scenario are
investigated when the gravitational coupling and the cosmological term
are not constant but rather there are time variation of them. From
observational point of view, these time variations are taken in the form
and . The behavior of scale
factors and different kinematical parameters are investigated for different
possible scenarios where the bulk cosmological constant can be
zero, positive or negative.Comment: RevTex, 7 figures, 16 page
Do olfactory and gustatory psychophysical scores have prognostic value in COVID-19 patients? A prospective study of 106 patients
Background: The lack of objective data makes it difficult to establish the prognostic value of chemosensitive disorders in coronavirus disease 2019 (COVID-19) patients. We aimed to prospectively monitor patients diagnosed with COVID-19 to see if the severity of olfactory and gustatory dysfunction associates with subsequent disease severity. Methods: Multicentre prospective study that recruited 106 COVID-19 subjects at diagnosis. Chemosensitive functions were assessed with psychophysical tests within 4 days of clinical onset, at 10 and 20 days. Daily body temperature and oxygen saturation were recorded as markers of disease severity alongside need for hospitalisation. The correlation between olfactory and gustatory scores and disease severity was assessed with linear regression analysis. Results: At T0, 71 patients (67%) presented with olfactory dysfunction while gustatory impairment was detected in 76 cases (65.6%). Chemosensitive disorders gradually improved over the observation period. No significant correlations were found between T0 chemosensitive scores and final disease severity. The correlation between olfactory scores and fever proved significant at T2 (p = 0.05), while the relationship with gustatory scores was significant at T1 (p = 0.01) and T2 (p < 0.001), however neither was clinically relevant. The correlation between chemosensitive scores and oxygen saturation was significant only for taste at T2 (p < 0.001). Logistic regression analysis found significant correlations between olfactory impairment severity and need for hospitalization at T2 (OR 3.750, p = 0.005). Conclusions: Initial objective olfactory and gustatory scores do not seem to have a significant prognostic value in predicting the severity of the COVID-19 course; however, persistence of olfactory dysfunction at 20 days, associated with a more severe course. Unfortunately, olfactory and gustatory dysfunction do not seem to hold prognostic value at the time of initial diagnosis
Effect of pre-existing baryon inhomogeneities on the dynamics of quark-hadron transition
Baryon number inhomogeneities may be generated during the epoch when the
baryon asymmetry of the universe is produced, e.g. at the electroweak phase
transition. The regions with excess baryon number will have a lower temperature
than the background temperature of the universe. Also the value of the quark
hadron transition temperature will be different in these regions as
compared to the background region. Since a first-order quark hadron transition
is very susceptible to small changes in temperature, we investigate the effect
of the presence of such baryonic lumps on the dynamics of quark-hadron
transition. We find that the phase transition is delayed in these lumps for
significant overdensities. Consequently, we argue that baryon concentration in
these regions grows by the end of the transition. We briefly discuss some
models which may give rise to such high overdensities at the onset of the
quark-hadron transition.Comment: 16 pages, no figures, minor changes, version to appear in Phys. Rev.
Non-renewal statistics in the catalytic activity of enzyme molecules at mesoscopic concentrations
Recent fluorescence spectroscopy measurements of single-enzyme kinetics have
shown that enzymatic turnovers form a renewal stochastic process in which the
inverse of the mean waiting time between turnovers follows the Michaelis-Menten
equation. Under typical physiological conditions, however, tens to thousands of
enzymes react in catalyzing thousands to millions of substrates. We study
enzyme kinetics at these physiologically relevant conditions through a master
equation including stochasticity and molecular discreteness. From the exact
solution of the master equation we find that the waiting times are neither
independent nor are they identically distributed, implying that enzymatic
turnovers form a non-renewal stochastic process. The inverse of the mean
waiting time shows strong departures from the Michaelis-Menten equation. The
waiting times between consecutive turnovers are anti-correlated, where short
intervals are more likely to be followed by long intervals and vice versa.
Correlations persist beyond consecutive turnovers indicating that multi-scale
fluctuations govern enzyme kinetics.Comment: 5 pages, 4 figures, to appear in Physical Review Letter
Search for nucleon decays with EXO-200
A search for instability of nucleons bound in Xe nuclei is reported
with 223 kgyr exposure of Xe in the EXO-200 experiment. Lifetime
limits of 3.3 and 1.9 yrs are established for
nucleon decay to Sb and Te, respectively. These are the most
stringent to date, exceeding the prior decay limits by a factor of 9 and 7,
respectively
Baryon inhomogeneity generation via cosmic strings at QCD scale and its effects on nucleosynthesis
We have earlier shown that cosmic strings moving through the plasma at the
time of a first order quark-hadron transition in the early universe can
generate large scale baryon inhomogeneities. In this paper, we calculate
detailed structure of these inhomogeneities at the quark-hadron transition. Our
calculations show that the inhomogeneities generated by cosmic string wakes can
strongly affect nucleosynthesis calculations. A comparison with observational
data suggests that such baryon inhomogeneities should not have existed at the
nucleosynthesis epoch. If this disagreement holds with more accurate
observations, then it will lead to the conclusions that cosmic string formation
scales above GeV may not be consistent with nucleosynthesis
and CMBR observations. Alternatively, some other input in our calculation
should be constrained, for example, if the average string velocity remains
sufficiently small so that significant density perturbations are never produced
at the QCD scale, or if strings move ultra-relativistically so that string
wakes are very thin, trapping negligible amount of baryons. Finally, if
quark-hadron transition is not of first order then our calculations do not
apply.Comment: 24 pages, 5 figures, minor changes, version to appear in Phys. Rev.
Cosmic string induced sheet like baryon inhomogeneities at quark-hadron transition
Cosmic strings moving through matter produce wakes where density is higher
than the background density. We investigate the effects of such wakes occurring
at the time of a first order quark-hadron transition in the early universe and
show that they can lead to separation of quark-gluon plasma phase in the wake
region, while the region outside the wake converts to the hadronic phase.
Moving interfaces then trap large baryon densities in sheet like regions which
can extend across the entire horizon. Typical separation between such sheets,
at formation, is of the order of a km. Regions of baryon inhomogeneity of this
nature, i.e. having a planar geometry, and separated by such large distance
scales, appear to be well suited for the recent models of inhomogeneous
nucleosynthesis to reconcile with the large baryon to photon ratio implied by
the recent measurements of the cosmic microwave background power spectrum.Comment: 8 pages, 3 figure
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